Monoterpenoids

Part I
TERPENOI DS
1
Monoterpenoids
BY R. B. YEATS
1 Introduction
This year's Report surveys the literature' up to August 1978, subject to its
availability in Europe2 by early November 1978. A few additional papers of
particular significance which were published between August and December
1978 have been included for added ~ l a r i t y Further .~ changes for this Report
concern halogenated mon~terpenoids~ and the consolidation of monoterpenoid
X-ray crystallographic structure determinations into a separate section. The
X-ray analysis of monoterpenoids has been increasing ~ignificantly.~
Unfortunately it is not always possible to identify such structure determinations in
earlier Reports.6 Since previous Reports' and lists' of X-ray structure deter-
minations were or i n a c c ~ r a t e ,it~ *
seems
~ timely to include in this
See Vol. 8, p. 3, ref. 1 for details of the literature coverage; 137 titles have been searched this year,
page-by-page, to yield approximately 2200 monoterpenoid-related papers; 1586 provide the core
upon which this Report is based. Compared to last year (Vol. 8, p. 3, ref. 2), 135 papers may be
computer-retrieved from the Essential Oils Section of Chemical Abstracts from September 1977 to
August 1978, whereas a total of 217 papers are retrievable under essential oils in all sections of
Chemical Abstracts during this period.
This Report is dedicated to Sir Derek Barton, F.R.S., in honour of his 60th birthday. The kind
hospitality and helpful encouragement extended by Sir Derek at the Institut de Chimie des
Substances Naturelles, Gif-sur-Yvette, France, during the preparation of this manuscript is acknow-
ledged with gratitude.
Literature available only as a Chemical Abstract after September 1st 1978 is not, however, included.
' Naturally occurring halogenated monoterpenoids have been placed in a new section this year. Since
many of them are now known to be cyclic compounds, it is no longer logical to classify them in the
acyclic section. Non-naturally occurring halogenated monoterpenoids, however, continue to be
reported in their respective sections.
Volumes 6,7, and 8 report 3,11, and 10 papers respectively, with a further 35 papers published this
year.
Examples where X-ray determinations are not identified include p-menth-l(7)-ene-trans-2,8-diol
(Vol. 2, p. 32, ref. 126) and bruceol (Vol. 7, p. 49, ref. 461).
For example, 2~~,4a-dibromo-lO~-pinan-3-one, P. P. Williams, Cryst. Structure Comm., 1973,2,1S,
has not been included previously in these Reports.
Vol. 5, pp. 206,207; for example, P-thujaplicin, J. E. Derry and T. A. Hamor, J.C.S. Perkin 11,1972,
694, is excluded from this list.
'Molecular Structures and Dimensions; Bibliography 1935-1969, General Organic Crystal Struc-
tures', ed. 0. Kennard and D. G. Watson, International Union of Crystallography, N.V.A.
Oosthoek's Uitgevers Mij Utrecht, 1970; thirteen out of thirty-two compounds listed under
monoterpenes are non-monoterpenoid. In contrast, thujic acid p-bromophenacyl ester" is not listed
as a monoterpenoid.
l o R. E. Davis and A. Tulinsky, J. Arner. Chern. SOC.,1966,88,4583.
3
4 Terpenoids a n d Steroids
new section references to all monoterpenoid X-ray crystal structure deter-

minations which have been reported in the literature to date.”
Authors are reminded of a request made earlier (Vol. 8, p . 4 ) concerning
sending reprints of monoterpenoid-related papers automatically to this Reporter
to assist the prompt compilation of future Reports.’
The restricted space available for these Reports unfortunately does not allow
the discussion of a number of topics of interest to monoterpenoid chemists; useful
reviews of such topics include monoterpenoid alkaloids,12 carbazole alkaloid^,'^
isoprenoids and alkaloids of tobacco,14 naturally occurring plant c o u m a r i n ~the
,~~
biosynthesis of aromatic hemiterpenes,16 and recent developments in the field of
naturally occurring aroma components. l 7 The poor quality of the Chemical
Abstracts” makes it difficult to assess the significance of a number of reviews of
potential industrial interest.” A volume in the ‘Methodicum Chimicum’ series
includes a very brief discussion of some monoterpenoids.20
Three useful reference works have been p ~ b l i s h e d . ~ ’ Some
- ~ ~ acyclic mono-
terpenoids containing one chiral centre are included in lists relating the sign of
optical rotation (no numerical values are given) and absolute stereochemistry
with the method of structural correlation; unfortunately the literature has only
been covered to 1971.21In contrast, Klein and Rojahn22have included literature
references to October 1976 in the literature report which accompanies their
wall-chart of monoterpenoid configurations. In an otherwise excellent and most
useful work, attention is drawn to four misprinted formulae [(+)-trans-myrtanol,
(-)-piperitenone epoxide, (+)-piperitone epoxide, and (-)-junionone] and the
omission of the iridoids, the naturally occurring halogenated monoterpenoids,
and some well-known cycloheptane monoterpenoids. It is always difficult to be
all-inclusive ; however, a significant number of monoterpenoids appear in only
one or the other of these works.21,22The graphic assembly of formulae22 from
Dragoco also illustrates the array of inconsistent nomenclature practices which
Most of these X-ray structure determinations have been published during the period covered by
these Reports; for the sake of completeness, 25 papers earlier than 1969 are included. This Reporter
would welcome hearing of structure determinations which have been omitted, so that they may be
included in future Reports.
I’ G. A. Cordell in ‘The Alkaloids, Chemistry, and Physiology’,ed. (the late) R. H. F. Manske, Vol. 16,
Academic Press, New York, 1977, Chapter 8, p. 431.
l 3 D. P. Chakraborty, Fortschr. Chem. org. Naturstoffe,1977, 34, 299.
14
C. R. Enzell, I. Wahlberg, and A. J. Aasen, Fortschr, Chem. org. Naturstoffe, 1977, 34, 1.
l5 R. D. H. Murray, Fortschr. Chem. org. Naturstoffe, 1978, 35, 199.
l 6 M. F. Grundon, Tetrahedron, 1978, 34, 143.
l7 G. Ohloff, Fortschr. Chem. org. Naturstoffe,1978, 35, 431.
l 8 Further to earlier criticism (Vol. 4, p. 3; Vol. 8, pp. 3, 4) of Chemical Abstracts, five examples of
duplicate abstracts have appeared this year; e.g. Volume 6 has been abstracted again, Chem. Abs.,
1977,87,168 257; cf. Chem. Abs., 1977,86,72 919.
( a )A. Nuerrenbach, Chem. LaborBerr., 1977,28,171 (Chem. A h . , 1978,88,121 390); ( b ) T .D. R.
Manning, Rep. N.Z., Dep. Sci. Ind. Res., Chem. Din, 1977, C.D. 2256 (Chem. Abs., 1978, 88,
121 394); ( c )T. Nishida, Y. Fujita, and K. Itoi, Sekiyu GakkaiShi, 1977,20,689 (Chem. Abs., 1978,
88, 7065); ( d ) H. Hikino, ibid., 1977, 20, 728 (Chem. Abs., 1978, 88, 7068).
*” ‘Methodicum Chimicum’, Vol. 11, pt. 3, ‘Steroids, Terpenes, and Alkaloids’, ed. F. Korte and M.
Goto, Academic Press, New York, 1978, p. 44: S. Hayashi, ‘Monoterpenoids and Sesquiterpenoids’.
J. Jacques, C. Gros, and S. Bourcier, ‘Absolute Configurations of 6000 Selected Compounds with
One Asymmetric Carbon Atom’, Vol. 4 of the series ‘Stereochemistry: Fundamentals and Methods’,
ed. H. B. Kagan, Thieme Verlag, Stuttgart, 1977.
’’ W. Rojahn and E. Klein, ‘Die Konfigurationen der Monoterpenoide’, Dragoco, Holzminden,
Germany, 1977; see p. 73 and refs. 144 and 658 for related comments.
Monoterpenoids 5
have grown up with the literature [e.g. thujone (isothujone), A4-carene (car-2-
ene), inconsistent o -menthane nomenclature, 2,6-dimethylocten-1 -diol-(3,8)
(cf. 3,7-dimethyloct-7-en- 1,6-diol), myrcenol us. myrcen-8-01]. Surely the time
has come to,adopt a standardized monoterpenoid nomenclature.
Few of the recently published reference books covering natural products
provide the chemist, within a single volume, with most of the detail which is
frequently required, uiz. names, structure, physical data, together with references
to occurrence, structure determination, and synthesis. The revised edition of
Karrer,23aand its first ~ u p p l e m e n t , ’do ~ ~provide this detail in their comprehen-
sive coverage of plant products. This strength makes these volumes indispensable,
despite the delay in covering the literature, uit. to 1956,23“and 1957-6123b
respectively. Newly isolated monoterpenoids now occupy a class of their own in
the first supplement, although some cycloheptane monoterpenoids (e.g. p-
dolabrin), quinones (e.g. /3 -thujaplicinol), and tetrahydrocannabinol (the formula
is incorrect) are listed ~ e p a r a t e l y . ’ ~ ~
2 Physical Measurements: X-Ray Crystallography; Chirality

X-Ray Crystallography.--In addition to 43 new structure determinations re-
ported this year, the list of X-ray structure determinations of monoterpenoids
(and closely related compounds falling within the scope of these Reports) which
follows includes compounds reported directly in earlier volumes (to which
references are made); original literature references are given for all other
structures, whether newly reported7*’*’’or not.6 The literature has been covered
from 1946 to August 1978.
2,6-Dimethyloctanes. Geranylamine h y d r ~ c h l o r i d e . ~ ~
Naturally Occurring Halogenated Monoterpenoids. (3R,4S,7S)-trans,trans-3,7-
Dimethyl-l,8,8-tribromo-3,4,7-trichloro-octa-1,5-diene (Vol. 7, p. 18, ref. 200) ;
violacene 2 (1;X = Cl) (Vol. 7, p. 19, ref. 209); costatol (Vol. 8, p. 31, ref. 301);
costatone (Vol. 8, p. 31, ref. 302); a reassigned structure for violacene (2);25
chondrocolactone (3);26 (lR,2S,4S,5R)-l,4-dibromo-5-chloro-2E-chlorovinyl-
1,5-dimethylcyclohexane (1; X = Br);27 and (lS,2S,4R,5S)-2-bromo-lE-
bromovinyl-4,5-dichloro-l,5-dimethylcyclohexane (4).27
Br
(1) L1 (2) (3) (4)

23 ( a ) W. Karrer, ‘Konstitution und Vorkommen der organischen Pflanzenstoffe (exklusive Alk-
aloide)’, 2nd edn., Birkhauser Verlag, Basel, Switzerland, 1976; ( b )W. Karrer, E. Cherbuliez, and C.
H. Eugster, ‘Konstitution und Vorkommen der orgmischen Pflanzenstoffe (exklusive Alkaloide)’,
Erganzungsband 1, Birkhauser Verlag, Basel; Switzerland, 1977.
24 D. W. J. Cruickshank and G. A. Jeffrey, Acta Cryst., 1954, 7 , 646.
” D. van Engen, J. Clardy, E. Kho-Wiseman, P. Crews, M. D. Higgs, and D. J. Faulkner, Tetrahedron
Letters, 1978, 29.
26 F. X. Woolard, R. E. Moore, D. Van Engen, and J. Clardy, Tetrahedron Letters, 1978, 2367.
” A. G . Gonzblez, J. M. Arteaga, J. D. Martin, M. L. Rodriguez, J. Fayos, and M. Martinez-Ripolli,
Phytochemistry, 1978, 17, 947.
6 Terpenoids and Steroids
Chrysanthernyl Derivatives and Pyrethrins. ( 1R,3R) - ( + )-trans- Chrysanthemic

acid p-bromoanilide (Vol. 7, p. 20, ref. 2 13);28(4s)-2-(prop-2’-enyl)rethron-4-
yl(lR,3R)-trans-chrysanthemate 6-bromo-2,4-dinitrophenylhydrazone (Vol. 4,
p. 20, ref. 115 incorrectly refers to the X-ray study of six pyrethrins)286(Vol. 5,
p. 15, ref. 102);28‘ a- cyano-3-phenoxybenzyl ci~-3-(2’,2’-dibromovinyl)-
2,2-dimethylcyclopropanecarboxylate;29 cis- 3 -phenoxybenzyl 3-(2’,2’-
di~romovinyl)-2,2-dimethylcyclopropanecarboxylate (Vol. 7, p. 10, ref. 1f9);
and cis-3-phenoxybenzyl 3-(2’,2’-dichlorovinyl)-2,2-dimethylcyclopropanecar-
boxylate (Vol. 7, p. 10, ref. 119).
Cyclopentanes, Irridoids, Monoterpenoid Alkaloids. ( - )-Bromodihydro-
umbellulone (5);30 ( - )-isoiridomyrmecin (6);3’ ( + )-iridomyrmecin (7) at
-150 0C;316*32 loganin penta-acetate r:,onomethyl ether the rubidium
salt dihydrate of monotropein (8; R = H);34(-)-sarracenin (Vol. 7, p. 27, ref.
269); ( -)-1-0-acetylxylomollin;34” (*)-gentiolactone (9);35 ( - )-jasminin
aglucone ethyl ether;3h tecomanine meth~perchlorate;~’ alkaloid C
m e t h i ~ d i d eand
; ~ ~nitropolyzonamine (10) per~hlorate.~’
@ @
H H
(8) (9) (10)

( a ) The X-ray analysis of the p-bromophenacyl ester of (lR,3R)-(+)-rran~-chrysanthemic
28 ester is
reported as a personal communication from G. Ferguson in the following; ( 6 ) M. J. Begley,
L. Crombie, D. J. Simmonds, and D. A. Whiting, J.C.S. Chem. Comm., 1972,1276 (Vol. 5,p. 206);
(c) J.C.S. Perkin I, 1974,1230.
29 J. D. Owen, J.C.S. Chem. Comm., 1974,859;see Vol. 7,p. 10,ref. 118 for the full paper.
30 H. E. Smith, R. T. Gray, T. J. Shaffner, and P. G. Lenhert, J. Org. Chem., 1969,34,136.
31 ( a ) B.P. Schoenborn and J. F. McConnell, Acta Cryst., 1962,15,779; ( 6 )J. F. McConnell, A. McL.
Mathieson, and B. P. Schoenborn, Tetrahedron Letters, 1962,445.The structure depicted in the
former for isoiridomyrmecin is incorrect.
32 J. F. McConnell, A. McL. Mathieson, and B. P. Schoenborn, Acta Cryst., 1964,17,472.
33 P. J. Lentz, jun. and M. G. Rossmann, J.C.S. Chem. Comm., 1969,1269; P.J. Lentz, jun., Diss. Abs.
Internat. ( B ) , 1971,32,715 (Vol. 5 , p. 206).
34 N. Masaki, M. Hirabayashi, K. Fuji, K. Osaki, and H. Inouye, Tetrahedron Letters, 1967,2367.
34aM.Nakane, C. R. Hutchinson, D. Van. Engen, and J. Clardy, J. Amer. Chem. SOC.,1978,100,7079;

see also ref. 462.
35 I. H.Suhr, P. Arends, and B. Jensen, Phytochemistry, 1978,17, 135.
36 A. Shimada and M. Fukuyo, Abstracts of the 22nd Japan Chemical Society Meeting, 1969,60,as
reported in Vol. 3,p. 28,ref. 141;Vol. 3,formula (105)lacks an 0-P-Glu group at C-1 (cf Vol. 6,
p. 26).
37 (a) G. Jones, G. Ferguson, and W. C. Marsh, J.C.S. Chem. Comm., 1971, 994 (Vol. 5, p. 206
incorrectly refers to p. 944);cf. Vol. 7,p. 28;( b ) G. Ferguson and W. C. Marsh, J.C.S. Perkin 11,
1975,1124.
38 R. W.Miller and A. T. McPhail, J. Chem. Res. ( M ) , 1978,901;(10)is a stereochemical revision of
the structure reported previously (Vol. 6,p. 13).
Monoterpenoids 7
p-Menthanes. (-)-Men thyl trimethylammonium iodide ;39 (-)-men thyl 4 -bromo-

2-nitroben~oate;~' (+)-isomenthy1 p -brom~phenylcarbamate;~~ the (-)-
menthoxyacetamide of (+)-trans-2- (0-bromophenyl)cyclohexylamine;42 (-)-
menthyl phenylgly~xylate;~~ (-)-menthy1 p-brom~phenylglyoxylate;~~ (-)-
menthyl (-)-p-iodobenzenes~lphinate;~~ (lR,3R,4S)-(-)-menthyl S-methyl
(S),-phenylphosph~nothioate;~~ (lR,3R,4S)-(-)-menthyl methyl (R),-phenyl-
p h ~ s p h o n a t e ; ~trans-dichlorobis(dimethylneomenthylphosphine)nickel(~~);~~
~
trans -dichloro bis(dime th ylneomen thylp hosphine)palladium(11) ;49 trans -
dichlorobis(dimethylmenthylphosphine)palladium(~~) ;49 (+)-a-naphthylphenyl-
1-men thoxymethoxysilane (4R,8R)- (+) -p-men th- 1-en-9-01 p-iodobenzo-
ate;" the diol (11);52(+)-cis-carvone t r i b r ~ m i d e 2,4-dibrom0menthone;~~
;~~
(11)
syn - and anti-pulegone toluene-p-sulphonylhydrazones;54" (+)-[(4S)-
carvone]Rh'(C,H,) ; 5 5 Fe(C0)3-pulegone racerni~,'~"*~
l a e ~ o - ,and
~~~'~
39 E. J. Gabe and D. F. Grant, Acta Cryst., 1962, 15, 1074; for earlier crystallographic data on this
compound, (-)-menthylamine hydrochloride, and (-)-menthylamine hydrobromide, see D. F.
Grant and D. Rogers, ibid., 1954,7, 301. An earlier paper, uiz. I. W. Ramsay and D. Rogers, ibid.,
1952, 5, 268, records data on a-I-menthol.
40*A.Itai, Y. Iitaka, U. Nagai, and Y. Kamo, Acta Cryst., 1976, B32, 1553.
" G. Kartha, K. T. Go, A. K. Bose, and M. S. Tibbetts, J.C.S. Perkin ZZ, 1976, 717.
'' T. G. Cochran, A. Weber, A. C. Huitric, A. Camerman, and L. H. Jensen, J. Org. Chem., 1976,41,
1640.
43 R. Parthasarathy, J. Ohrt, A. Horeau, J. P. Vigneron, and H. B. Kagan, Tetrahedron, 1970,26,4705
(Vol. 5, p. 206).
'' J. M. Ohrt and R. Parthasarathy, Acta Cryst., 1969, A25, S198; J. Cryst. Mo:. Structure, 1975,5,359.
45 E. B. Fleischer, M. Axelrod, M. Green, and K. Mislow, J. Arner. Chem. SOC.,1964,86, 3395.
46 J. Donohue, N. Mandel, W. B. Farnham, R. K. Murray, jun., K. Mislow, and H. P. Benschop, J.
Amer. Chem. Soc., 1971, 93, 3792. Vol. 5, p. 206 incorrectly refers to a thiolate.
47
W. B. Farnham, K. Mislow, N. Mandel, and J. Donohue, J.C.S. Chem. Comm., 1972, 120.
48 K. Kan, Y. Kai, N. Yasuoka, and N. Kasai, Bull. Chem. SOC.Japan, 1977, 50, 1051.
49 K. Kan, K. Miki, Y. Kai, N. Yasuoka, and N. Kasai, Bull. Chem. SOC. Japan, 1978,51, 733.
J. A. Kanters and A. M. van Veen, Cryst. Structure Comm., 1973, 2, 261; for an earlier crystallo-
graphic study of the racemic compound, see J.-P. Vidal, J.-L. Galignt, and J. Falgueirettes, Compt.
rend., 1970, 270, C, 690 (Vol. 5 , p. 206).
5 1 J. F. Blount, B. A. Pawson, and G. Saucy, J.C.S. Chem. Comm., 1969, 715; the formula of
(4R,8R)-p-menth-l -en-9-d is depicted incorrectly in this paper.
" W. E. Scott and G. F. Richards, J. Org. Chem., 1971,36, 63; W. E. Scott, Diss. Abs. Znternat. ( B ) ,
1970, 31, 157 (Vol. 5, p. 206 incorrectly refers to p. 170).
53 R. W. Schevitz and M. G. Rossmann, J.C.S. Chem. Comm., 1969,711; R. W. Schevitz, Diss. Abs.
Znternat. ( B ) ,1971,31,4533 (Vol. 5, p. 206).
54 J. A. Wunderlich and W. N. Lipscomb, Tetrahedron, 1960, 11, 219.
54a J. F. Blount, and reported in W. G. Dauben, G. T. Rivers, and W. T. Zimmerman, J. Amer. Chem.
Soc., 1977, 99, 3414 and G. T. Rivers, Diss. Abs. Znternat. (B), 1978, 38, 3700. This WBS first
reported in Vol. 7 , p. 34, ref. 341; however, the chirality at C-1 has not been stated.
5 5 W. Winter, B. Koppenhofer, and V. Schurig, J. Organometallic Chem., 1978,150, 145.
56 E. Koerner von Gustorf, F.-W. Grevels, C. Kriiger, G. Olbrich, F. Mark, D . Schulz, and R. Wagner,
2. Naturforsch., 1972, 27b, 392 (Vol. 5, p. 206).

57 ( a ) Vol. 7, p. 29, ref. 287; ( b )J. Kroon, P. R. E. van Gurp, H. A. J. Oonk, F. Baert, and R. Fouret,
Acta Cryst., 1976, B32, 2561; (c) F. Baert, M. Foulon, and R. Fouret, 3rd European Crystallo-
graphic Meeting, 6th-10th September 1976, Zurich, Switzerland, Collected Abstracts, p. 215; ( d )
F. Baert, R. Fouret, H. A. J. Oonk, and J. Kroon, Acta Cryst., 1978, B34, 222.
m i x e d - ~ r y s t a carvoxime;
l ~ ~ ~ ~ ~ optically race mi^,^^^^^" and solid-solution
of benzoylcarvoxime; diplatinum tetra(dithi0cumate) ;" dibromode-
hydrobispulegone;60 monobromoisodehydrobispulegone;61and the monoter-
penoid-related tri-o -thymitide and some clathrates.62
m-Menthanes. 3,CY -Dimethyls t yrene-[Fe (C0),l2
Cycluheptanes. Thujic acid p-bromophenacyl ester;1° p-thujaplicin;" 3,5,7- tri-
bromohinokitiol;63" 3,7-dibrornohinokiti01;~~~ 5,7-dibromohinokiti01;~~~
y-
t hu j aplicin ;64 and the di-isopropyldi tropolonofuran u tahin .64a*65
Bicyclo[2,2, llheptanes. (+)-Camphor;"" ( - )-," (+)-,"" and (f)-camphoroxime;"*
(+)-3-bromocamphor (Vol. 2, p. 38);6" (+)-8-bromocamphor (Vol. 8, p. 49,
ref. 439); endo-3,9-dibromocamphor;70 3-exo,9,9-tribromocamphor [Vol. 7, p.
37, ref. 372; formula (179) should have an exo-3-bromo-group]; (+)-3-endo,
9,9-tribromocamphor (Vol. 8, p. 50, ref. 442); (+)-camphor-3-carboxylic
acid;70" (+)-3-p-bromobenzylidenecamphor;71 (+)-" and (*)-o-chloro-
phenylirnin~carnphor;~~~ (f)-trans-r-camphanic acid (Vol. 3, p. 67, ref. 293);
(+)-3-diazocamphor (Vol. 3, p. 62, ref. 269); (-)-2-exo-bromo-2-endo-nitro-
~ a m p h a n e ;(+)-lO-bromo-2-exo
~~ -chloro-2-endo - n i t r o s ~ c a m p h a n e ; 2-exo-
~~
bromo-2-endo- nitr~fenchane;~' 6-endo- b r o m o i s ~ f e n c h o n e(-)-1,7-dibromo-
;~~
3,3,4-trimethylnorbornan-2-one (Vol. 8, p. 49, ref. 440); 1,7-dibromo-4-
dibromomethyl-3,3-dimethylnorbornan-2-one (Vol. 8, p. 50, ref. 441); 2-endo-
58 F. Baert, J.-P. Mornon, and P. Herpin, Compt. rend., 1971, 273, C , 231.
" J. P. Fackler, jun., J. Amer. Chem. SOC., 1972, 94, 1009 (Vol. 5, p. 206).
6o A. Perales, S. Martinez-Carrera, and S. Garcia-Blanco, Acta Cryst., 1969, B25, 1817.
61 S. Martinez-Carrera and J. M. Franco, Acta Cryst., 1972, A28, S20; J. M. Franco, S. Martinez-
Carrera, and S. Garcia-Blanco, ibid., 1974, B30,415. The incorrect nomenclature used in this paper
was later corrected; see Vol. 7, p. 29, ref. 288. See also ref. 525.
62 S. Brunie and G. Tsoucaris, Cryst. Structure Comm., 1974, 3, 481; S. Brunie, A. Navaza, and
.G. Tsoucaris, Acta Cryst., 1975, A31, S127; D. J. Williams and D. Lawton, Tetrahedron Letters,
1975,111.
62n F. H. Herbstein and M. G. Reisner, J.C.S. Chem. Comm., 1972, 1077; see formula (166).
S. It& Y. Fukazawa, and Y. Iitaka, Tetrahedron Letters, ( a )1972,741; ( b )1972,745. The authors use
the name hinokitiol in preference to (3-thujaplicin.
64 ( a ) A.-C. Wiehager, B. Karlsson, and A.-M. Pilotti, 2nd European Crystallographic Meeting,
26th-29th August 1974, Heszetely, Hungary, Collected Abstracts, p. 573; ( b ) Vol. 8, p. 48, ref.
423.
b5 B. Karlsson. A.-M. Pilotti, and A.-C. Wiehager, Acta Cryst., 1976, B32, 3118.
66 H. A. J. Oonk, Ph.D. Thesis, Utrecht, 1965.
67 F. Baert and R. Fouret, Acta Cryst., 1978, B34, 2546.
'* F. Baert, R. Fouret, and C. Gors, 4th European Crystallographic Meeting, 30th August-3rd
September 1977, Oxford, England, Abstracts B, p. 522.
69 F. H. Allen and D. Rogers, J. Chem. SOC.( B ) , 1971,632. For earlier reports, see F. H. Allen and
D. Rogers, J.C.S. Chem. Comm., 1966, 837 and M. G. Northolt and J. H. Palm, Rec. Trav. chim.,
1966,85,143.An earlier paper also reports X-ray data for a-chloro- and a-cyano-camphor; viz. E.
H. Wiebenga and C. J. Krom, ibid., 1946, 65, 663.
70 K. L. Brown and D. Hall, Cryst. Structure Comm., 1973, 2, 659.
70aA.Baptista, Anais Acad. brasil. Cienc., 1977,48, 223 (Chem. Abs., 1977,87, 125 684).
71 J. J. Bonnet and U. Jeannin, Krist. und Tech., 1973,8, 133 (Chem. Abs., 1973,79,71 146).
7 2 (a) F. Baert, M. Foulon, and R. Fouret, Cryst. Structure Comm., 1975,4,61;( b )M. Foulon, F. Baert,
and R. Fouret, ref. 57c, p. 279.
73 D. A. Brueckner, T. A. Hamor, J. Monteath Robertson, and G. A. Sim, J. Chem. SOC., 1962,799.
74 G. Ferguson, C. J. Fritchie, J. Monteath Robertson, and G. A. Sim, J. Chem. Soc., 1961, 1976.
75
C. RCrat, Compt. rend., 1968, 266, C , 612; for an earlier report, see J. Berthou, Y. Brunel,
A. Laurent, A. Rassat, and C. Rerat, ibid., 1967, 264, C , 292 (Vol. 5 , p. 207).
76 P. P. Williams, Chem. and Ind., 1964, 1583; Acta Cryst., 1969, B25, 409.
Monoterpenoids 9
bromo-6-exo(dimethylaminomethyl)fenchane hydr~bromide;~’ anhydro-

bromonitrocamphane ( (-)-camphene-8-carboxylic acid;79 (+)-iso-
camphenilanic acid p -bromophenacyl ester;79a(k)-carbocamphenilone;” syn -

2,2’-bifenchylidene E at -120 O C ; ” l-biapocamphane;82 N- (S)-phenyl-
alaninato[(+)-hydroxymethylidenecamphorato]copper(~~);’~bis-(3-nitrocam-
phorato)-(2-methylpyridine)copper(11);84 A-( +)ss9-truns-tris-[(+)-3-acetyl-
camphorato]chromium(~~~);~~ (1R,2S,3S,aR)- 3 -(a- hydroxybenzyl)-l,7,7-tri-
methylbicyclo[2,2,1]heptan-2-ol;86 (1R,3S,aR)- 3-(a- hydroxybenzy1)-l,7,7-
trimethylbicyclo[2,2,1]heptan-2-one;s7(2R)-(-)- 2- [(lS’,2R’)- 1’,3’-dithian-2’-
yl]isoborneol l’-oxide;88 and 2,2,5-endo,6-exo,8,9,10-heptachlorobornane.89
Many papers (e.g.see Vol. 5,p. 207) have confirmed the absolute configuration of
(+)-3-endo -bromocamphor-9-sulphonic acid;” likewise a number of papers
have established the absolute configuration of (+)-camphor-10-sulphonic acid as
various For the isoalbene S-benzylthioether (189; X = SCH,Ph) (endo-
2,6-dimethyl-4-benzylthiotricyclo[5,2,1 ,02*6]dec-3-ene)see ref. 611b.
Bicyclo [3,1, llheptunes. 2a,4a- Dibromo- lop -pinan-3-0ne;~ (-)-cis-pinocar-
veyl p-nitrobenzoate (Vol. 5, p. 36, ref. 269); the cyclic sulphite of lop-
77 ( a )G. Reck, 2.Chem., 1969,9,30; ( b )L. Kutschabsky and G. Reck, J. prukt. Chem., 1971,312,896
(Vol. 5, p. 207).
78 G. L. Dwivedi and R. C. Srivastava, Actu Cryst., 1972, B28, 2567.
79 P. C. Moews, J. R. Knox, and W. R. Vaughan, J. Amer. Chem. Soc., 1978,100,260;see Vol. 8, p. 49,
ref. 438 for a preliminary publication. For further discussion of this compound, (184; X = H,H;
Y = E-CHCHO,H), see p. 66.
79a J. M. Midgley, W. B. Whalley, G. Buchbauer, G. W. Hana, H. Koch, P. J. Roberts, and G. Ferguson,
J.C.S. Perkin I, 1978, 1312; see formula (183; X = exo-COZCHzCOC6H4Br-p).
80
B&ee, J. P. Seymour, and A. W. Burgstahler, J.C.S. Chem. Comm., 1974,235; for the full paper, see
Vol. 8, p. 49, ref. 437.
81
T. Pilati and M. Simonetta, J.C.S. Perkin II, 1977, 1435.
82
R. A. Alden, J. Kraut, and T. G. Traylor, J. Amer. Chem. Soc., 1968,90, 74.
83
L. Casella, M. Gullotti, A. Pasini, G. Ciani, M. Manassero, and A. Sironi, Znorg. Chim. Acru, 1978,
26, L1. Personal communication from the authors indicates that the last two lines of the fourth
paragraph should read ‘agreement indices are R = 0.045 and Rw = 0.055 for the correct enan-
tiomorph and R = 0.050 and Rw = 0.061 for the other’.
84
G. Dessy and V. Fares, Cryst. Structure Comm., 1977,6, 583.
85
W. Dew. Horrocks, jun., D. L. Johnston, and D. MacInnes, J. Amer. Chem. Soc., 1970, 92, 7620
(Vol. 5, p. 207).
86
R. L. Harlow and S. H. Simonsen, Cryst. Structure Comm., 1976,5, 791.
87
R. L. Harlow and S. H. Simonsen, Cryst. Structure Comm., 1976, 5,471.
88
R. F. Bryan, F. A. Carey, 0.D. Dailey, jun., R. J. Maher, and R. W. Miller, J. Org. Chem., 1978,43,
90.
89
K. J. Palmer, R. Y. Wong, R. E. Lundin, S. Khalifa, and J. E. Casida, J. Amer. Chem. SOC.,1975,97,
408.
90
J. A. Wunderlich, Acru Cryst., 1967, 23, 846 (Vol. 5, p. 207).
91
For example, see G. R. Brubaker and L. E. Webb, J. Amer. Chem. SOC., 1969, 91, 7199;
C. Couldwell, K. Prout, D. Robey, R. Taylor, and F. J. C. Rossotti, Actu Cryst., 1978, B34, 1491.
~ i n a n e - 2 , 3 a - d i o l ; ~ ~3-(N-methylaminomethyl)pinane hydr~bromide;~~
3 - (N,N-dimethy laminomethy1)pin-2 ( 10)-ene hydro bromide ;94 (-) -bromo-
derivative of paeoniflorin (Vol. 3, p. 71, ref. 308); (+)-bis-(T-pineny1)nickel
(Vol. 3, p. 71, ref. 310; Vol. 6, p. 41, ref. 307); (+)-Fe(CC)3-pinocarvone
complex;56 the phosphetan (-)-(13) which is synthesized from (-)-a-pinene
(13)
and MePC12-AlC13;95 (-)-(lS,5S)-6,6-dimethyl-2-[(2'S)-3',3',3'-trichloro-2'-
hydroxypropyl]bicyclo[3,1,l]hept-2-ene tosylate ester (cf Vol. 8, p. 54);96 3-
c h l o r ~ n o p i n o n e ; ~and
~ " 3-brom0nopinone.~~"
Cannabinoids and other Phenolic Monoterpenoids. (-)-Bruce01 (14; X = OH,
Y = H);97 (-)-bromobruceol (14; X = OH, Y = Br);98 (*)-dibromodeoxybruceol
(15; X = Br);97 an acetylcitran [Vol. 7, p. 48, formula (255)]99 and the cor-
responding f ~ r m y l c i t r a ndibromocannabicyclol(16);'oo
;~~ murrayazoline ( 17);'01
cyclocymopol monomethyl ether acetate (Vol. 7, p. 48, ref. 454); xanthochymol
(Vol. 8, p. 60, ref. 536) and the related isoxanthochymol di-p-bromoben-
zenesulphonate;lo2 ~annabinol;"~~annabidiol;"~6P-hydroxy-A1-THC-DMF
complex at -165 0C;'05A'-tetrahydrocannabinolic acid B (Vol. 6 , p. 49, ref. 362);
cannabispiran;lo6and the synthetic cannabinoid derivative 8,5a-trans-5a,9a-cis-
y2 M. J. Brice, J. M. Coxon, E. Dansted, M. P. Hartshorn, and W. T. Robinson, J.C.S. Chem. Comm.,
1969, 356. For related discussion of this compound, see Vol. 8, p. 9 (cf. Vol. 1, p. 43).
93 G. Reck and L. Kutschabsky, Acta Cryst., 1970, B26, 578.
94 L. Kutschabsky, 2. Chem., 1969,9, 31; for the full paper see ref. 77b.
95 E. Vilkas, M. Vilkas, D. Joniaux, and C. Pascard-Billy, J.C.S. Chem. Comm., 1978, 125.
y6 M. J. Begley, G. B. Gill, and B. Wallace, J.C.S. Perkin I, 1978, 93; see formula (209) for the parent
alcohol.
96aY.Barrans, Compt. rend., 1964, 259, 796.
97 M. J. Begley, L. Crombie, D. A. Slack, and D. A. Whiting, J.C.S. Chem. Comm., 1976, 140; J.C.S.
Perkin f, 1977,2402. In the latter there is a discrepancy between the crystallographic models and the
formulae which are used; the absolute configuration was not determined, however.
98 A. M. Duffield, P. R. Jefferies, E. N. Maslen, and A. I. M. Rae, Tetrahedron, 1963, 19, 593.
99
M. J. Begley, L. Crombie, R. W. King, D. A. Slack, and D. A. Whiting, J.C.S. Chem. Comm., 1976,
138; J.C.S. Perkin I, 1977, 2393. In the latter, formulae (4) and (5) are misprinted.
loo M. J. Begley, D. G. Clarke, L. Crombie, and D. A. Whiting, J.C.S. Chem. Comm., 1970,1547; W. M.
Bandaranayake, M. J. Begley, B. 0. Brown, D. G. Clarke, L. Crombie, and D. A. Whiting, J.C.S.
Perkin I, 1974, 998.
lo' J. Bordner, D. P. Chakraborty, B. K. Chowdhury, S. N. Ganguli, K. C. Das, and B. Weinstein,
Experientia, 1972,28,1406.See ref. 100 and Vol. 5, p. 45 for related chemistry. In the latter, formula
(255) lacks a methyl group at C-4 and its name is spelled incorrectly; it should be murrayazolidine.
C. G. Karanjgoakar, A. V. Rama Rao, K. Venkataraman, S. S. Yemul, and K. J. Palmer, Tetrahedron
Letters, 1973, 4977. See, however, ref. 705.
T. Ottersen, E. Rosenqvist, C. E. Turner, and F. S. El-Feraly, Acta Cnem. Scand., 1977, B31,781.
( a )P. G. Jones, L. Falvello, 0. Kennard, G. M. Sheldrick, and R. Mechoulam, Actu Cryst., 1977,
B33, 3211; (6) T. Ottersen, E. Rosenqvist, C. E. Turner, and F. S. El-Feraly, Acta Chem. Scand.,
1977, B31, 807.
l o 5 T. Ottersen and E. Rosenqvist, Acta Chem. Scand., 1977, B31, 749.
lo6 Vol. 7, p. 49, ref. 667; F. S. El-Feraly, M. A. Elsohly, E. G. Boeren, C. E. Turner, T. Ottersen, and
A. Aasen, Tetrahedron, 1977,33, 2373.
Monoterpenoids 11
(16) (17)
(Vol. 6,
1,8-dimethyl-5a-isopropyl-5a,6,7,8,9,9a-hexahydrodibenzofuran-3-ol
p. 49, ref. 363).
Miscellaneous. Mustelan 1,l-dioxide (Vol. 7, p. 8, ref. 88); trans-
[PtCl(CH2=C-CMe=CH2)(PPh3)2];'07 trans- [Pt(CH,=C-CMe=CH,)
(C_=C-CMe=CH,)(PPh3)2];'07
2,7-dirnethyloctane-2,7-diol tetrahydrate;'"
trans -2,7-dimethylocta-2,4,6- triene- 1:4,5 :8-diolide. O9
Spectral and other Physical Data.-The 1: 1 adduct camphor-[Eu(dpm),] illus-

trates a simple balanced linear regression method for obtaining the equilibrium
constant (K)for adduct formation and the limiting chemical shifts, corresponding
to complete complexation, for each methyl group; K values determined from
data for each methyl group agree very closely.'1o A useful method for preparing
small quantities of anhydrous n.m.r. solvents has been published."' A two-
dimensional Fourier-transformation technique for correlating 'H and 13Cchem-
ical shifts, based upon long-range spin-spin coupling, may be used to identify
gem -dimethyl groups (e.g. menthone, camphor) by observing the 'H spectra
arising from modulated 13C signals.'12 The assignment of 13C resonances by
off-resonance decoupling may be improved by scaling down the proton-carbon
splittings to optimum values (e.g.the C-3 triplet and C-4 doublet components for
c a m p h ~ r ) . ' '13C
~ N.m.r. data are reported for some monoterpenoid 1,3-dithians
107
A. Furlani, M. V. Russo, A. C. Villa, A. G. Manfredotti, andC. Guastini, J.C.S. Dalton, 1977,2154.
108
G. A. Jeffrey and D. Mastropaolo, Acta Cryst., 1978, B34,552.
109
A. Colombo and G. Allegra, Acta Cryst., 1966, 21, 124.
110
3.. Bouquant and J. Chuche, Bull. Soc. chim. France, 1977,959.
111
J. B. Alper, Analyt. Chem., 1978, 50, 381.
'12 G.Bodenhausen and R. Freeman, J. Amer. Chem. Soc., 1978, 100, 320.
R. Freeman and G. A. Morris, .L Magn. Resonance, 1978,29, 173.
[citral, citronellal, perillaldehyde, myrtenal, menthone, isopulegone, and carvone

(18)], 1,3-dithiolans [citronellal, menthone, isopulegone, (IS)], and dithiol
Michael-adducts [isopulegone, (1 S)]. '14 y-Shift correlations are of value in

assigning hydroxy- and bromo-substituent group stereochemistry adjacent to
axial methyl or gem-dimethyl groups in substituted c y c l ~ h e x a n e s . ~Further
'~
n.m.r. data are reported below in the discussion o n absolute configuration and
optical purity, as well as in individual sections.
Some monoterpenoid stereoisomers (e.g. the pinenes, geraniols, borneols, and
menthols) are readily distinguished by ion kinetic energy spectroscopy.116
Further discussion of c.d. calibration using (+)-camphor-10-sulphonic acid has
been published (cf. Vol. 8, p. 5).'17 A c.d. investigation of charge-transfer
complexes between chiral donors and tetracyanoethylene, dichlorodicy-
anoquinone, and Vitamin K, includes data on monoterpenoids [e.g. (-)-
fenchone, (+)-camphor, (+)-3-endo-bromocamphor, (-)-a-pinene, (-)-
menthol]; n + T * and T + T * transitions were also investigated in a vapour-phase
and solvent-dependent c.d. study of, inter alia, (+)-pulegone, (-)-carvone [(4R)-
(18)], (-)-fenchone, and (+)-camphene-l-carboxaldehyde."8
Further papers in this section report intramolecular hydrogen-bonding in
2-arylaminomethylenecycloalkanones (menthone, carvomenthone, camphor),l''
the effect of chlorinated solvents on the stability constants of hydrogen-bonded
complexes between pyrrole and, inter alia, fenchone,12' and a correlation of
half-wave oxidation potentials with the pK, values of the corresponding con-
jugate acids (e.g. 3 -endo-cyano~amphor).~*~
Absolute Configuration, Optical Purity, Asymmetric Synthesis, Resolution.-

Reviews of interest in this section concern methods of determining absolute
A. Hoppmann, P. Weyerstahl, and W. Zummack, Annaien, 1977, 1547.

P. Crews and E. Kho-Wiseman, Tetrahedron Letters, 1978, 2483; see ref. 426 for an application.
' I 6 S . Eguchi, K. Nagai, M. Nakayama, and S . Hayashi, Shitsuryo Bunseki, 1976,24,295 (Chem. Abs.,
1977,87, 135 984).
G . C. Chen and J. T. Yang, Analyt. Letters, 1977, 10, 1195.
' 1 8 M. Houtan, Diss.Abs. Internat. ( B ) , 1978, 38, 5381.
'I9 V. N. Gogte, C. I. Jose, A. G . Namjoshi, Y. D. Vankar, and B. D. Tilak, Indian J. Chem., 1977,15B,
778.
'*" J. Monteau, H. Huser, M. Guerin, and M. Gomel; ( a )J. Chem. Res. ( S ) , 1978,256; ( b )J. Chem. Res.
( M ) ,1978, 3217. The former implies that camphor is used in this study but the latter only refers to
fenchone.
12' J. M. Kern and P. Federlin, Tetrahedron, 1978, 34, 661.
Monoterpenoids 13
configurations, 122 discriminating interactions between chiral strat-

egies in optical resolutions,124and asymmetric
Yamaguchi has extended the use of [Eu(fod),] with Mosher’s reagent esters (cf.
Vol. 8, p. 4), to the determination of absolute configuration and enantiomeric
purity of primary alcohols which are chiral at the adjacent carbon. However,
methoxy peak separation for (4R,8R)-(+)-p-menth-l-en-9-01 does not allow
enantiomeric purity determination.126The determination of absolute configura-
tion and of stereoisomeric composition for enantiomeric (cf. ref. 126b) and
diastereomeric (cf.Vol. 8, p. 4)secondary alcohols profits from better resolution
’ ~ ~ for determining the absolute configuration of
in the 19Fn.m.r. ~ p e c t r u m . Rules
secondary alcohols (e.g. menthol) by observing 13C n.m.r. glycosidation shifts
have been proposed (cf. Vol. 8, p. 40).’**
In contrast, Horeau has developed a simple kinetic method for determining the
enantiomeric purity and absolute configuration of chiral secondary alcohols (e.g.
menthol) based upon enantioselective esterification with a -phenylbutyric anhy-
dride of known enantiomeric purity. 129 Cholesteric phase formation on adding
small amounts (<1 mg) of chiral molecules to nematic has been used to
determine absolute configurations of molecules possessing one asymmetric
carbon atom (uia i.r. rotatory dispersion); the sign of the R-Cotton effect
correlates well with absolute configurations [e.g. carvone (IS), pulegone,
limonene] expressed in ligand volume priority.’30h
For the determination of the enantiomeric composition of some chiral acidic
monoterpenoids, see the chromatography section below.
The optical purity of chiral lactones [e.g. (19)] follows from ‘H n.m.r. obser-
vation, in the presence of tris[trifluoromethylhydroxymethylene-(-)-
camphorato]europium(~~~), of the diols derived from treatment with methyl-
122
‘Stereochemistry: Fundamentals and Methods’, ed. H. B. Kagan, Thieme Verlag, Stuttgart, 1977;
( a ) Volume 1: ‘Determination of Configurations by Spectrophotometric Methods’; (b) Volume 2:
‘Determination of Configurations by Dipole Moments, CD, or ORD’; (c) Volume 3: ‘Determination
of Configurations by Chemical Methods’.
123
D. P. Craig and D. P. Mellor, Fortschr. Chem. Forsch., 1976, 63, 1.
124
S. H. Wilen, A. Collet, and J. Jacques, Tetrahedron, 1977, 33, 2725.
125
D. Valentine, jun. and J. W. Scott, Synthesis, 1978, 329.
126
( a ) F. Yasuhara and S. Yamaguchi, Tetrahedron Letters, 1977, 4085; ( 6 ) an earlier paper,
S. Yamaguchi, F. Yasuhara, and K. Kabuto, Tetrahedron, 1976, 32, 1363, concerning secondary
alcohols, was inadvertently omitted from these Reports.
127
A. J. Van de Wal, E. M. Merckx, G. L. Lemikre, T. A. Van Osselaer, J. A. Lepoivre, and F. C.
Alderweireldt, Bull. SOC. chim. belges, 1978,87, 545.
128
S. Seo, Y. Tomita, K. Tori, and Y. Yoshimura, J. Amer. Chem. Soc., 1978,100, 3331.
129
A. Schoofs and A. Horeau, Tetrahedron Letters, 1977, 3259; cf. Vol. 8, p. 8, ref. 70.
130
( a ) E.-H. Korte, B. Schrader, and S. Bualek, J. Chem. Res. ( S ) , 1978, 236; see also E.-H. Korte,
B. Schrader, S. Bualek, and H.-J. Krabbe, Angew. Chem. Internat. Edn., 1977, 16, 790;
(b) H.-J. Krabbe, H. Heggemeier, B. Schrader, and E.-H. Korte, ibid., 1977,16,791; J. Chem. Res.
( S ) , 1978,238.
1 i t h i ~ m . l ~The
' enantiomeric compositions of oxaziridines derived from
camphor132may be determined133by 'H n.m.r. in the presence of 2,2,2-trifluoro-
1-arylethanols, extending an earlier ~ u g g e s t i o n ; these
' ~ ~ papers also report an
enzymic synthesis of (R)- (-) -2,2 2 -trifluoro- 1 -a-naph thyle thanol (76 YO optical
and asymmetric induction in oxaziridine formation using ( S ) - ( + ) -
monoperoxycamphoric The latter may be compared with results obtained
using rn-chloroperoxybenzoicacid where in the presence of (R)-(-)-menthol the
degree of asymmetric induction in oxaziridine formation is much less than in the
presence of (S)-(+)-2,2,2-trifluoro-l -phenylethan~l.'~~
Asymmetric epoxidation of alkenes using H 2 0 2and the dehydrating agent (20;
x = 2, Y = CO) is only marginally better than with monoperoxycamphoric acid
(20)
(however, cf. Vol. 8, p. 7);136in contrast, epoxidation with t-butyl hydroperoxide
in the presence of chiral vanadium or molybdenum complexes, e.g. bis-[(+)-3-
trifluoroacetylcamphorato]dioxomolybdenum, proceeds with no asymmetric
indu~tion.'~'An extension of previous work (Vol. 6, p. 6; Vol. 7, p. 4; Vol. 8, p. 7)
is double asymmetric induction which uses a chiral NAD(P)H model system to
reduce (R)-(-)-menthy1 ben~oy1formate.l~~ This has also been reduced with
NaBH,-chiral phase-transfer catalyst although asymmetric induction was not
always consistent with the Prelog rule (cf. Vol. 8, p. Further examples of
asymmetric homogeneous rhodium hydrogenation c a t a l y ~ t s illustrate
~ ~ ~ ~ ' ~the
~
potential of using chiral bidentate ligands.141 Hydroboration-oxidation of cis-
alkenes with monoisopinocampheylborane (IPCBH2) and with di-iso-
pinocampheylborane (IPC2BH),both derived from (+)-pinene, yields alcohols of
opposite stereochemistry in -20% and 295% optical yields The
preparation of IPCBH2 has been optimized.'43The simple to IPCBH2
turns out to be a relatively long and time-consuming process;143gmethods of
synthesis have proceeded through treatment of the complex Et3N-IPCBH2143b*c
131
I. J. Jakovac and J. B. Jones, J.C.S. Chem. Comm., 1978,722.
132
For another (uncited) report of these oxaziridines as well as those derived from (-)-menthylamine,
see D. Mostowicz and C. Belzecki, J. Org. Chem., 1977, 42, 3917.
133
A. Forni, I. Moretti, and G. Torre, Tetrahedron Letters, 1978, 2941.
134
W. H. Pirkle and P. L. Rinaldi, J. Org. Chem., 1977, 42, 3217.
135
A. Forni, I. Moretti, and G. Torre, J.C.S. Chem. Comm., 1977, 731.
136
J. Rebek: S. Wolf, and A. Mossman, J. Org. Chem., 1978, 43, 180.
137
C. Dobler and E. Hoft, 2. Chem., 1978,18, 218.
138
A. Ohno, T. Kimura, S. G . Kim, H. Yamamoto, S. Oka, and Y. Ohnishi, Bioorg. Chem., 1977,6,21.
139
R. Kinishi, Y. Nakajima, J. Oda, and Y. Inouye, Agric. and Biol. Chem. (Japan), 1978,42, 869.
140
G. Paiaro and L. Pandolfo, Gazzetta, 1977,107,467.
141
M. Fiorini, F. Marcati, and G. M. Giongo, J. Mol. Catalysis, 1978, 4, 125.
142
A. K. Mandal and N. M. Yoon, J. Organometallic Chem., 1978,156,183; cf. Vol. 8, p. 6, ref. 4 4 and
Vol. 8, p. 7, ref. 47.
143
( a ) Vol. 8, p. 7, ref. 47; (b) Vol. 8, p. 6, ref. 44; (c) Vol. 8, p. 6, ref. 45; ( d ) H. C . Brown and A. K.
Mandal, Synthesis, 1978, 146; ( e ) Vol. 8, p. 7, ref. 48; (f) B. Singaram and J. R. Schwier, J.
Organometallic Chem., 1978, 156, C1; ( g ) H . C. Brown, J. R. Schwier, and B. Singaram, J. Org.
Chem., 1 9 7 8 , 4 3 , 4 3 9 5 .
Monoterpenoids 15
with BH3,THF1436or better with BF3,Et20in pentane to the rapid

preparation of IPC2BH143a*e which is converted into a crystalline bis-adduct with
N,N,N',N'-tetramethylethylenediamine'43ffrom which optically pure IPCBH2is
liberated on treating with BF3,Et20 in THF. 143g Palladium(I1)-catalysed asym-
metric oxidative cyclization of 2-allylphenols is achieved in the presence of
(-)-P-pinene; similar optical yields (12%) are observed with bisracetoxy-(10,2,
3-q-pinene)palladium(11)]~ a t a 1 y s i s . The
l ~ ~ full paper of an earlier report of D-
amino-acid synthesis (Vol. 7, p. 4) demonstrates the superior chiral directing
ability. of Schiff bases derived from (lS,2S,SS)-(-)-2-hydroxypinan-3-0ne'~~
over those derived from (-)-menthone. 146 Enantioselective carbenoid cyclo-
propanation (Vol. 8, p. 7) has been described in Regioselectivity to
terminal double bonds in some conjugated olefins with up to 88% enantioselec-
~ "not been improved upon with the use of additional monoterpenoid-
t i ~ i t y ' ~has
cobalt mechanistic details and control of enantioselectivity have
also been In contrast, the decomposition of chiral diazoacetates
[e.g. (+)-bornyl, (-)-menthy11 by CuCl proceeds with low asymmetric
induction. 148
Further examples of asymmetric reactions involving chiral monoterpenoids
include the formation of chiral /3 -keto-sulphoxides from (-)-menthy1 carboxy-
lates,I4' synthesis of diastereomeric tetrahedral molybdenum complexes,15othe
enantioselective hydrosilylation of ketone^,"^ and the preparation of the chiral
1-amino-2-phenylethylphosphonic
Interesting examples of optical resolutions include the use of dicarbonyl-
rhodium(1) 3-trifluoroacetyl-( lR)-camphorate for g.1.c. separation of chiral
01efins'~~ and of dimeric nickel(I1) bis-(3-trifluoroacetyl-lR -camphorate) for an
improved separation of chiral epoxides (cf. Vol. 8, p. 8).154The resolution of
(R/S)-pantoic acid with chiral amines derived from a- and p-pinene (Vol. 7,
p. 43, ref. 420) may signal their more widespread use.1551,3-Dithian 1-oxide has
been
Chromatography.-G.1.c. papers of interest include the separation of monoter-

penoid hydrocarbons on modified graphitized carbon the separation of
T. Hosakawa, S. Miyagi, S.-I. Murahashi, and A. Sonoda, J.C.S. Chem. Comm., 1978, 687.
Unfortunately the authors name this catalyst bis[acetoxy-(7,1,2-~-pinene)palladium(11);other
poorly numbered compounds are recorded in ref. 22.
14' T. Oguri, N. Kawai, T. Shioiri, and S.-I. Yamada, Chem. and Pharm. Bull. (Japan), 1978,26,803.
146 T. Oguri, T. Shioiri, and S.-I. Yamada, Chem. and Pharm. Bull. (Japan), 1977,25,2287.
147 ( a )A.Nakamura, A. Konishi, Y. Tatsuno, and S. Otsuka, J. Amer. Chem. SOC.,1978,100,3443; (b)
A. Nakamura, A. Konishi, R. Tsujitani, M. Kudo, and S . Otsuka, ibid., 1978,100,3449.For earlier
reports see (c) A. Nakamura, Pure A p p l . Chem., 1978,50,37;( d )Vol. 8,p. 7;( e ) Y. Tatsuno, A.
Konishi, A. Nakamura, and S . Otsuka, J.C.S. Chem. Comm., 1974,588, which was inadvertently
omitted from an earlier Report.
148 P. E. Krieger and J. A. Landgrebe, J. Org. Chem., 1978,43,4447.
149 N. Kunieda, H. Motoki, and M. Kinoshita, Chem. Letters, 1978,713.
H.Brunner and J. Doppelberger, Chem. Ber., 1978,111,673.
M . Capka, Coll. Czech. Chem. Comm., 1977,42,3410.The asymmetric hydrosilylation of alkenes is
reported in ref. 49.
A. Kotynski and W. J. Stec, J. Chem. Res. ( S ) , 1978,41.
V.Schurig, Angew. Chem. Internat. Edn., 1977,16,110;this paper was inadvertently omitted from
last year's Report.
V. Schurig and W. Burkle, Angew. Chem. Internat. Edn., 1978,17,132.
"' J. Paust, S. Pfohl, W. Reif, and W. Schmidt, Annalen, 1978,1024.
A. Di Corcia, A. Liberti, C. Sambucini, and R. Samperi, J. Chromatog., 1978,152,63.
menthol isomers,157and further work by Scheffer et al. on the prefractionation of

monoterpenoids by liquid-solid column chromatography before g.1.c. separa-
tion.15' H.p.1.c. resolution of chiral acids [e.g. ( 3-RS)-dihydrocitronellic acid,
(3-RS)-7-methoxycitronellic acid] is now reported via (R)-(+)-1-(1'-naph-
thy1)ethylamide derivatives (cf. Vol. 8, p. 22).159
3 General Synthetic Reactions

Some useful reviews'" which discuss applications from, or are of value to,
monoterpenoid chemistry concern recent applications of the retro-Diels-Alder
reaction in organic synthesis,161the Claisen rearrangement,'62 intramolecular ene
reactions,163the Prins chiral insect pheromones (synthesis, absolute
configuration, and optical p ~ r i t y ) , ' ' ~
the synthesis of monoterpenoids using the
Wittig reaction,Ih6the introduction of fluorine into organic organo-
selenium chemistry,168bromination using 2,4,4,6-tetrabromocyclohexa-2,5-di-
enone (in Japanese),169titanium tetrachloride in organic 4-dialkyl-
aminopyridines as acylation catalysts,171the use of insoluble polymer supports in
organic selective reactions with organoaluminium
and organic reactions on a 1 ~ m i n a . ICorey ~~ has expanded computer-assisted
synthetic analysis to include stereoselective olefin synthesis. 175
As the search for new synthetic methods continues, there has been a substantial
increase in the number of papers reporting the use of monoterpenoids as model
compounds. Some of the more significant examples of such synthetic methods
provide the basis for the following discussion.
The ene reaction (of, for example, the pinenes) with P h S 0 2 N S 0 has been
~ ~ the cyclization-induced [3,3] sigmatropic rearrangement of
d e ~ c r i b e d , 'and
allylic carbamates (e.g. linalyl N,N-dimethylcarbamate) catalysed by mercuric
Is7 H. Thieme and R. Benecke, Zentralbl. Pharm., Pharmakother. Laboratoriumsdiagn., 1977,116,139.
Is8 J. J. C. Scheffer, A. Koedam, M. Th. I . W. Schiisler, and A. Baerheim Svendsen, Chromatographia,
1977, 10, 669 and references therein.
l S 9 ( a ) B. J. Bergot, R. J. Anderson, D. A. Schooley, and C. A. Henrick, J. Chromatog., 1978,155,97;
( b ) C. A. Henrick, R. J. Anderson, G. B. Staal, and G . F. Ludvik, J. Agric. Food Chem., 1978,26,
542.
160
Recent reviews of interest to organic chemists are listed as a new regular feature in Journal of Organic
Chemistry. For reviews published in 1977, see J. Org. Chem., 1978,43,3085; a second list covering
the first half of 1978 has appeared recently, uir. ibid., 1978, 43, 4397.
161 J. L. Ripoll, A. Rouessac, and F. Rouessac, Tetrahedron, 1978, 34, 19.
I h 2 G. B. Bennett, Synthesis, 1977, 589.
W. Oppolzer and V. Snieckus, Angew. Chem. Internat. Edn., 1978, 17, 476.
164 D. R. Adams and S. P. Bhatnagar, Synthesis, 1977, 661.
16' R. Rossi, Synthesis, 1978, 413.

M. S. Bathia, Riechst., Aromen, Kosmet., 1977, 27, 205.
M. Schlosser, Tetrahedron, 1978, 34, 3.
"* D. L. J. Clive, Tetrahedron, 1978, 34, 1049.
169 T. Kato, I. Ichinose, and T. Hosogai, J. Synth. Org. Chem., Japan, 1977, 35, 491.
170 T. Mukaiyama, Angew. Chem. Internat. Edn., 1977, 16,817.
171 G. Hofle, W. Steglich, and H. Vorbruggen, Angew. Chem. Internat. Edn., 1978, 17,569.
( a ) C. C. Leznoff, Accounts Chem. Res., 1978, 11, 327; (b) P. Hodge, Chem. in Britain, 1978, 14,
237.
1 7 3 H. Yamamoto and H. Nozaki, Angew. Chem. Internat. Edn., 1978,17, 169.
' 7 4 G. H. Posner, Angew. Chem. Internat. Edn., 1978, 17,487.
'71 E. J. Corey and A. K. Long, J. Org. Chem., 1978,43,2208.

176 G. Deleris, J. Kowalski, J. Dunogues, and R. Calas, Tetrahedron Letters, 1977, 421 1; see also refs.
216. 498.
Monoterpenoids 17
trifluoroacetate avoids skeletal rearrangement in the 60% overall conversion of

linalool into geraniol and nerol(7 : 3).17' The [3,3] sigmatropic rearrangement of
allylic thionocarbamates to allylic thiolcarbamates (Vol. 8, p. 25) has been used
further to synthesize acids and esters (e.g. geranic esters E :2 / 3 : 1)via mercury-
catalysed cleavage of a,a -bis-sulphenylated derivatives; alkylation of the cor-
responding a -monosulphenylated derivative leads similarly to The
rearrangement of unsaturated cyclohexenones [e.g. carvone (1S)], catalysed by
RhC1,,3H20 (cf. Vol. 8, p. 9) results in aromatization; corresponding imines
behave ~ i m i 1 a r l y .Whereas
l~~ simple allylic alcohols rearrange in high yield to the
corresponding aldehydes and ketones using [(cod)1r(PMePh2),]PF6, rearrange-
ment of nerol is poor.18oA simple 1,2-carbonyl transposition (e.g. menthone to
carvomenthone) results from an epoxidation-LiAlH, reduction-chromic acid
oxidation sequence on enol silyl ethers (cf.Vol. 8, p. 53).181
Although the investigation of oxidative methods continues, it is apparent that
Swern's'82 is usually the method of choice for the oxidation of alcohols to
aldehydes and ketones (e.g. the borneols, 182b geranio1'82c) in high to essentially
quantitative yields (cfiVol. 8, p. 10). Other methods include the use of barium
manganate (the borneo1s),lg3 oxidation of alkoxymagnesium bromides using
N-chlorosuccinimide, rn -chloroperbenzoic acid, diacetoxyiodobenzene (e.g.
menthol), or, best of all, 1,l'-(azodicarbony1)dipiperidine [geraniol yields citral
(96'/0)].'~~The oxidation of monoterpenoid allylic alcohols using 2,3-dichloro-
5,6-dicyano- 1,4-benzoquinone has been d e ~ c r i b e d . 'The ~ ~ failure to oxidize
unsaturated silyl ethers with N-bromosuccinimide contrasts with results (Vol. 7,
p. 6) on the corresponding tributylstannyl ethers, despite acceptable yields with
saturated silyl ethers.lS6The economical vicinal cis-hydroxylation of alkenes (e.g.
citronellyl acetate) using Et4N' OAc--t-butyl peroxide in acetone, catalysed by
osmium tetroxide, has been the corresponding regiospecific vicinal
cis -oxyamination has been achieved in pyridine or CH2C12(e.g. citronellyl methyl
ether) by treatment with trioxo(t-alkylimido)osmium(vIII) leading to carbon-
nitrogen bond formation at the least-substituted carbon atom.188Allylic methyl
oxidation of acetals and tetrahydropyranyl ethers using S e 0 2in pyridine has been
177 L. E. Overman, C. B. Campbell, and F. M. Knoll, J. Amer. Chem. Soc., 1978, 100, 4822.
'71 T. Nakai, T. Mimura, and T. Kurokawa, Tetrahedron Letters, 1978, 2895.
179 P. A. Grieco and N. Marinovic, Tetrahedron Letters, 1978, 2545.
''O D. Baudry, M. Ephritikhine, and H. Felkin, Nouueau J. Chim., 1978, 2, 355.
''I W. E. Fristad, T. R. Bailey, and L. A. Paquette, J. Org. Chem., 1978, 43, 1620.
'" ( a ) S. L. Huang, K. Omura, and D. Swern, Synthesis, 1978, 297; ( 6 ) K. Omura and D. Swern,
Tetrahedron, 1978,34,1651; (c) A. J. Mancuso, S.-L. Huang, andD. Swern, J. Org. Chem., 1978,43,
2480.
l B 3 H. Firouzabadi and E. Ghaderi, Tetrahedron Letters, 1978, 839; the borneols [a mixture of
(+)-borne01 and (-)-isoborneol was used] and camphor each lack the C-10 methyl group in this
paper.
lB4 K. Narasaka, A. Morikawa, K. Saigo, and T. Mukaiyama, Bull. Chem. Soc. Japan, 1977,50,2773;
for related oxidations from these workers, see Vol. 7, p. 6.
lS5 J.-I. Iwamura, Nippon Kagaku Kaishi, 1978,846;for related work on saturated alcohols, see Vol. 4,
p. 6 and Vol. 8, p. 10.
lB6 H. W. Pinnick and N. H. Lajis, J. Org. Chem., 1978, 43, 371.
K. Akashi, R. E. Palermo, and K. B. Sharpless, J. Org. Chem., 1978, 43, 2063.
''' D. W. Patrick, L. K. Truesdale, S. A. Biller, and K. B. Sharpless, J. Org. Chem., 1978,43,2628. Two
closely related papers (no monoterpenoid examples) report major improvements in this process, viz.
E. Herranz and K. B. Sharpless, ibid., 1978,43,2544; E. Herranz, S. A. Biller, and K. B. Sharpless,
J. Amer. Chem. SOC.,1978,100, 3596.
examined.ls9 Enolates may be converted directly into a -hydroxy-ketones (e.g.

3 -endo -hydroxycamphor) using M O O ~ - ~ ~ - H M P A ; thermal
'~' intermediate
fragmentation may lead to some camphorquin~ne,~~' which is also a major
by-product in attempted conversion of thiocamphor into camphor using ben-
zeneseleninic anhydride as reagent. 19' The highly regioselective addition of
phenylselenenic acid ['PhSeOH', or more probably PhSeOSePh or
PhSeOSe(O)Ph, generated in situ from PhSe02H and PhSeSePh] followed by
treatment with t-butyl hydroperoxide results in a one-pot synthesis of rearranged
allylic alcohols (e.g. 8-methoxy-2,6-dimethyloct-3-en-2-ol from citronellyl
methyl ether).192The same paper also explores the catalytic effectiveness of
various seleninic acids (0-nitro- and 2,4-dinitro-phenylseleninic acids are the
most effective) in olefin (e.g. citronellyl methyl ether) epclxidation using 30%
H 2 0 2in the presence of anhydrous MgS04. Regioselectivity studies on geraniol
differ somewhat from those reported earlier (Vol. 8, p. ll).'92 Photochemical
co-oxygenation of alkenes and acetaldehyde with moltx-ular oxygen produces
epoxides (e.g. from a- and B-pinene) effectively and with reported regioselec-
tivity (1,2-epoxy-p-menth-8-enefrom limonene; 98'/0);'~~t-pentyl hydro-
pero~ide-Mo(C0)~ has been used for epoxidizing silicon-containing alkenes (e.g.
9-trimethyl~ilyl-p-rnenth-l-ene).'~~ Methods for deoxygenating epoxides
using Me~(OPh)J-BF,,Et,O-MeCN (epoxycitronellyl methyl ether)lQ5and
(EtO),P(O)Te Na' [limonene diepoxide yields 1,2-epoxy-p-menth-8-ene
(76'/0)]'~~have been reported; in the latter, the reagent may be generated
continuously in situ using a catalytic amount of tellurium. 196 NaOH-modified
alumina favours the rearrangement of epoxides to allylic alcohols.'97
Allylic alcohols are the almost exclusive products of the rapid reduction of
a$-unsaturated ketones [e.g. (4R)- (-)- (18), pulegone (21), piperitone] using
(21)
NaBH4-CeC13,6H20-Me0H;'98
like the parent 9-BBN, B-(1,2-dimethyl-
propyl)-9-borabicycl0[3,3,1 Jnonane also produces allylic alcohols exclusively
from qp-enals (e.g. ~ i t r a l )The ~ paper on the exclusive reduction of the
. ~ ~full
lS9 F. Camps, J. Coll, and A. Parente, Synthesis, 1978, 215.
I9O E. Vedejs, D. A. Engler, and J. E. Telschow, J. Org. Chem., 1978, 43, 188.
lgl D. H. R. Barton, N. J. Cussans, and S. V. Ley, J.C.S. Chem. Comm., 1978, 393.
19* T. Hori and K. B. Sharpless, J. Org. Chem., 1978, 43, 1689.
193 H. Kropf and M. R. Yazdanbakhch, Synthesis, 1977,711.
194 I. A. Gailyunas, E. M. Tsyrlina, N. I. Solov'eva, N. G. Komalenkova, and V. P. Yur'ev, J. Gen. Chem.
(U.S.S.R.),1977,47,2188. However, see ref. 181; this compound is incorrectly named in the paper.
195 K. Yamada, S. Goto, H. Nagase, Y. Kyotani, and Y. Hirata, J. Org. Chem., 1978,43,2076.
196 D. L. J. Clive and S. M. Menchen, J.C.S. Chem. Comm., 1977,658.
'91 V. S. Joshi and S. Dev, Tetrahedron, 1977, 33, 2955; for further discussion, see the bicy-
clo[3,1 ,l]heptane and the bicyclo[4,1,0]heptane sections.
19' J.-L. Luche, L. Rodriguez-Hahn, and P. Crabbb, J.C.S. Chem. Comm., 1978,601.
199 M. M. Midland and A. Tramontano, J. Org. Chem., 1978, 43, 1470. This reagent is probably most
valuable for the preferred reduction of aldehydes in the presence of ketones.
Monoterpenoids 19
olefinic double bond of a,P -unsaturated carbonyl compounds [e.g. (18)]reports

improved yields using Naz[Fe(C0)4]-Fe(CO)5-HOAc-dioxancompared with
Na[HFez(C0)8];200 trialkylammonium formate-Pd/C also performs this reaction
efficiently [citral to citronella1 (910 / ~ ) ] . 2 0 ' Reductions (e.g. of camphor) with
various magnesium hydrides give predictable stereochemical results.202Azodi-
carboxylate may be used to reduce carbon-carbon double bonds in cyclic
peroxides (e.g. ascaridole to d i h y d r o a s c a r i d ~ l e ) Selective
.~~~ catalytic hydro-
genations Include reduction of a,@-unsaturated ketones to saturated ketones [e.g.
(18) to dihydrocarvone] using K3C~(CN)5204 or [ R h ( b i ~ y ) ~ion20s
]+ as catalyst,
and the exocyclic double bond reduction in limonene over Ni-P.*06 Elec-
troreductive syntheses involve the conversion of P -hydroxy-sulphone groups
derived from lactones [e.g. (19)] or aldehydes (e.g. citronellal) into vinyl groups2o7
and the similar conversion of @ -hydroxy-sulphides derived from ketones (e.g.
menthone).208 Electroreduction of the corresponding y-hydroxy-sulphide
mesylates (22; R = H or Me), which are readily obtained from citral, provides an
efficient route to the cyclopropanes (23; R = H or Me) respectively.209A less
efficient a,@-unsaturated aldehyde-cyclopropane conversion involves Birch
reduction of (22; R = H) to (23; R = H).210Interestingly, no cyclopropanes [e.g.
(23; R = Me)] result from Simmons-Smith reaction when citral reacts with
CH212-Zn-Me3A1.207b Alicyl esters (e.g. bornyl acetate) are reduced to alkanes in

reasonable yields (quantitatively for tertiary esters) using Na-HMPA-Bu'OH.211
200
J. P. Collman, R. G. Finke, P. L. Matlock, R. Wahren, R. G. Komoto, and J. I. Brauman, J. Amer.
Chem. SOC.,1978,100, 11 19; see Vol. 7, p. 7 for the earlier report. The authors also make a useful
comparison with other methods for performing this reaction.
201
N. A. Cortese and R. F. Heck, J. Org. Chem., 1978,43, 3985.
202
E. C. Ashby, A. B. Goel, and J. J. Lin, Tetrahedron Letters, 1977, 3133; E. C. Ashby, J. J. Lin, and
A. B. Goel, J. Org. Chem., 1978,43, 1560, 1564; cf Vol. 7, p. 7 .
203
W. Adam and H. J. Eggelte, Angew. Chem. Internat. Edn., 1977, 16, 713.
204
G. S. R. Subba Rao, J. Rajaram, S. Rathnamala, and R. Sivaramakrishnan, Proc. Indian Acad. Sci.,
1977,86A, 435.
205
G. Mestroni, R. Spogliarich, A. Camus, F. Martinelli, and G. Zassinovich, J. Organornetallic Chem.,
1978,157,345;conditions for reduction to carvotanacetone, carvomenthone, or dihydrocarveol are
also described.
206
K. Isogai, S. Ageishi, and H. Ojima, J. Synth. Org. Chem., Japan, 1977, 35, 750.
207 ( a )T. Shono, Y. Matsumura, and S. Kashimura, Chem. Letters, 1978,69; ( b )much better yields for
methylenation of citral are obtained using CH212-Zn-Me3Al whereas for ketones (e.g. camphor)
CH2Br2-Zn-TiC14 is preferred: K. Takai, Y. Hotta, K. Oshima, and H. Nozaki, Tetrahedron Letters,
1978,2417.
208 T. Shono, Y. Matsumura, S. Kashimura, and H. Kyutoku, Tetrahedron Letters, 1978, 2807.
2"9 T. Shono, Y. Matsumura, S. Kashimura, and H. Kyutoku, Tetrahedron Letters, 1978,1205; formula
(11) is incorrect in this paper.
210 Y.-H. Chang, D. E. Campbell, and H. W. Pinnick, Tetrahedron Letters, 1977, 3337.
* 1 1 H. Deshayes and J.-P. Pete, J.C.S. Chem. Comm., 1978, 567.
Reductive deoxygenation of alcohols using Ireland’s method212a has been

improved for sterically hindered alcohols (e.g. LY -terpineol) by an improved
synthesis of N,N,N’,N’-tetramethylphosphorodiamidates;212b straightforward
modification of the method allows alkene and alkyl chloride formation [depend-
ing upon whether the alcohol is primary, secondary (e.g. menthol), or tertiary (e.g.
cy -terpineol)] without affecting such acid-sensitive groups as a ~ e t a l s The.~~~
well-known reductive cleavage of enol phosphates212a(cf. Vol. 8, p. 45) to
alkenes ( e , g . camphor to born-2-ene) has been improved by the use of titanium
Reductive deoxygenation of tosylhydrazones [ e . g . pulegone (21)] may
also be accomplished (cf. Vol. 6, p. 9; Vol. 7, p. 7) using NaBH4-HOAc, although
in somewhat lower Allylic deuteriation [e.g. P-pinene, (4R)-(-)-(18),
citronellyl methyl ether] results from ene reaction with TsN=S=O followed by
retro-ene reaction after deuterium exchange of the derived acidic NH proton (cf.
Vol. 7, p. 8).216The susceptibility of fenchone to hydride transfer without
accompanying carbanion addition has been used in dehydrogenative aromatiza-
tion (by deprotonation-hydride elimination) with fenchone and a catalytic
amount of potassium fencholate; olefin formation is only possible with appreci-
ably acidic C H
A number of papers report enolate alkylation and related procedures. They
include the regiospecific generation of lithioenamines from a$ -unsaturated
imines [e.g. from (18)Jand subsequent alkylation as an alternative to reductive
alkylation of enones,218reductive alkylation of epoxy-ketones (e.g. 1,6-epoxy-
carvone) using M ~ , C U L ~ - M ~ I - H M P theA , ~regioselective
~~ alkylation of di-
epoxides (e.g. limonene diepoxide), using R(CN)CuLi, at the least hindered
oxiran,220and reductive a -methylsulphenylation in moderate yield of cyclic
cy,P-unsaturated ketones [e.g. (IS)], via pseudoaxial attack, using dimethyl
disulphide.221” Although attempts222 to improve upon reductive cy - phenyl-
sulphenylation22’bof a,@-unsaturated ketones [e.g. (18)] by using diethyl-
aluminium cyanide were unsuccessful and the intermediacy of the ,8 -cyano-
silylenol ether offered no improvement in yield, treatment of the p-cyanosilylenol
ether with methyl-lithium results in an effective net 1,4-addition of an acetyl
anion equivalent to an enone.222Related work includes the conversion of
aldehydes (e.g. citronellal) and ketones into their (Y -phenylseleno-derivatives via
the silylenol ether and phenylselenenyl the quantitative tri-
’12 ( a )See Vol. 3, p. 312, ref. 126; ( b )H.-J. Liu, S. P. Lee, and W. H. Chan, Canad. J. Chem., 1977,55,
3797.
’13 H.-J. Liu, W. H. Chan, and S. P. Lee, Chem. Letters, 1978, 923.
’14 S. C. Welch and M. E. Walters, J. Org. Chem., 1978, 43, 2715.
215 R.0. Hutchins and N. R. Natale, J. Org. Chem., 1978, 43, 2299.
216 T. Hori, S. P. Singer, and K . B. Sharpless, J. Org. Chem., 1978, 43, 1456; for closely related ene
reactions, see refs. 176, 498.
’” M. T. Reetz and F. Eibach, Angew. Chem. Internat. Edn., 1978, 17,278.
218 P. A . Wender and M. A. Eissenstat, J. Amer. Chem. SOC., 1978, 100, 292.
‘I9 R. P. Szajewski, J. Org. Chem., 1978,43, 1819; for similar work, see Vol. 2, p. 26.
*” R.-D. Acker, Tetrahedron Letters, 1978, 2399.
221 ( a )P. G. Gassman, D . P. Gilbert, and S. M. Cole, J. Org. Chem., 1977,42,3233;( 6 )for related work,
see M. Samson, H. D e Wilde, and M. Vandewalle, Bull. SOC.chim. belges, 1977,86, 329.
222 M. Samson and M. Vandewalle, Synth. Comm., 1978,8,231; no physical data are reported for the
acetyl derivative and reference 3 of this paper is incorrect.
223 I. Ryu, S. Murai, I. Niwa, and N. Sonoda, Synthesis, 1977, 874; facile cyclization of a-phenyl-
selenocitronellal is also reported.
Monoterpenoids 21
phenylphosphine-catalysed 1,4-addition of phenyl trimethylsilyl selenide to a,@-

unsaturated ketones [e.g. (18 ) y 4and the highly regiospecific Markovnikoff -
addition of phenylselenenyl chloride to alkenes (e.g. a -terpineol, cis- and trans-
rose oxides) at -50 0C.225Alkylation of allylic nitriles (e.g. geranyl and neryl
nitriles) followed by reductive decyanation of the corresponding &?-unsaturated
nitriles yields tetrasubstituted alkenes efficiently.z26The generation of vinyl-
lithium reagents and subsequent trapping with electrophiles (including Vilsmeier
formylation) has been described in detailzz7and a two-step procedure, consisting
of anti-Markovnikoff thiophenol addition to monosubstituted alkenes (e.g.
limonene) followed by lithium cleavage, effects regiospecific hydrolithiation to
form alkyl-lithiums.228 The formation of .rr-allylpalladium complexes from
alkenes [e.g. (18),methyl geranate, @ - ~ i n e n e ] effectively
~~~= activates an allylic
C-H bond for subsequent allylic alkylation (aided by phosphorus ligands) with
various synthetically useful n ~ c l e o p h i l e s ,e.g.
~ ~ anions
~ ~ * ~ from malonic acid (Vol.
6, p. 4 9 , P-keto-sulphides, P-keto-sulphoxides (Vol. 6, p. 9), and P-keto-
sulphones. Alkylative elimination involving thermal sulphenic acid elimination
readily yields c,P-y,S-unsaturated esters (Vol. 6, p. 9), and prenylation with
MeZC=CH-C=(COzMe)SO2Ph can be used to transform monoterpenoids into
the corresponding sesquiterpenoids.2z9c Other prenylation procedures which
have been reported include Lewis acid-catalysed reaction of
Me3SiCMe2CH=CH2 with acetals and with ketones (regiospecific transposition
of the allylic double bond is and the Bu:N’ F--catalysed reaction of
Me3SiCHzCH=CMe2 with aldehydes and ketones (no double-bond trans-
position is observed);231however, Me3SiCHzCH=CMe2undergoes regiospecific
transposition of the allylic double bond in the A1C13- or BF3,Etz0-catalysed
monoallylic substitution, and also in the TiC14-catalysed diallylic substitution or
conjugate addition-substitution, of a$-unsaturated a~etals.’~’3,3-Dimethyl-
allyl(dipropy1)borane adds to aldehydes with double-bond and
prenylation of dithians (e.g. from citronellal, citral, perillaldehyde, and myrtenal)
has been reported using prenyl as well as prenylation of anions
formed from senecioamides, with control over a- and y- prenylation depending
224 D. Liotta, P. B. Paty, J. Johnston, and G. Zirna, Tetrahedron Letters, 1978,5091.

*” D. Liotta and G. Zima, Tetrahedron Letters, 1978,4977.
226 J. A.Marshall and R. Bierenbaum, J. Org. Chem., 1977,42,3309.
227 A. R. Chamberlin, J. E. Sternke, and F. T. Bond, J. Org. Chem., 1978,43, 147;in the case of
camphor, reaction is best with the 2,4,6-tri-isopropylbenzenesulphonylhydrazone.For related work,
see Vol. 6,p. 7;Vol. 7,p. 36.In the latter, reference to camphor was inadvertently omitted. See also
ref. 635.
’” C. G. Screttas and M. Micha-Screttas, J. Org. Chem., 1978,43,1064.
’” ( a )B. M. Trost, P. E. Strege, L. Weber, T. J. Fullerton, andT. J. Dietsche, J. Amer. Chem. SOC.,1978,
100,3407;B.M.Trost, L. Weber, P. E. Strege, T. J. Fullerton, and T. J. Dietsche, ( b ) ibid., 1978,
100,3416; ( c ) 1978,100,3426. Unfortunately, inattention to detail in the numbering of compounds
(lo),(12),and (13)in ref. 229c results in errors in relating the experimental section with the main text
and in equations 3-9.
230 A. Hosomi and H. Sakurai, Tetrahedron Letters, 1978,2589.
231 A.Hosomi, A. Shirahata, and H. Sakurai, Tetrahedron Letters, 1978,3043.
232 A.Hosomi, M. Endo, and H. Sakurai, Chem. Letters, 1978,499.
233 B. M.Mikhailov, Yu. N. Bubnov, A. V. Tsyban, and M. Sh. Grigoryan, J. Organometallic Chem.,
1978,154,131.
234 A. Hoppmann and P. Weyerstahl, Tetrahedron, 1978,34,1723.
upon the use of lithiated or cuprated species re~pectively.~~’ Regioselective

y-alkylation of allylic alcohols (e.g. geraniol, linalool) to yield alkenes
(stereoselectively in appropriate examples) may be accomplished by the action of
N-methyl-N-phenylaminotributylphosphonium iodide on allyloxy-CuRLi
The stereoselective elaboration of an acetylenic bond into the
corresponding E-2-methylalkenylalane by regioselective addition of Me3Al-
zirconocene dichloride (C12ZrCp2),237followed by known functionalization,
yields esters (e.g. ethyl geranate), alcohols (e.g. geraniol), carboxylic acids, and
methyl ethers very effectively.237cThe straightforward carbanionic addition of
a -phenylthioacetate to ketones and a$-unsaturated ketones [e.g. ( and
the one-step synthesis of nitriles from ketones (e.g. 2-cyanocamphane from
camphor) using tosylmethyl isocyanide have been cis -2-Ethoxy-
vinyl-lithium (prepared by hydrostannation of ethoxyacetylene) is a useful
nucleophilic acetaldehyde equivalent for the chain extension of aldehydes (e.g.
geranial) and ketones into a,P -unsaturated aldehydes.240Two groups241report a
similar interconversion in modifications of the Wittig-Horner reaction; for
example, the direct addition of the dianion of (EtO),P(0)CH2C02Hto aldehydes
and ketone^,^^^^'^ a reaction also reported s u b ~ e q u e n t l y , ~yields * -
~ ~ ~ ~ a,@
unsaturated carboxylic acids stereoselectively [e.g. geranic acid (E :2 / 4 : l)].241b
The corresponding diethyl carboxylchloromethylphosphonate dianion yields, for
example, a-chlorogeranic
Alkenes (e.g. camphene) are readily prepared242by the BF3,Et20-catalysed
elimination of secondary borate Terminal conjugated dienes may be
prepared by Pd(OAc),-PPh,-catalysed elimination from ally1 phenyl ethers or
allylic acetates [e.g. geranyl, neryl, and linalyl acetates to form similar mixtures of
myrcene (60-74%), trans-ocimene (8-20°/0), and cis-ocimene (14-20Y0)],~~~
and the complex [(q-C5H5)Cr(N0)2]2 dehalogenates vic -dihalides (e.g. limonene
tetrabromide) without affecting other halides (except for benzyl halides).245
235 J. A. Oakleaf, M. T . Thomas, A. Wu, and V. Snieckus, Tetrahedron Letters, 1978, 1645. For similar
LY- and y-selectivity with a$-unsaturated acids and esters, see Vol. 7, p. 14.
236 Y. Tanigawa, H. Ohta, A. Sonoda, and S.-I. Murahashi, J. Amer. Chem. SOC.,1978, 100,4610.
237 ( a )D. E. Van Horn and E.-I. Negishi, J. Amer. Chem. SOC.,1978,100,2252;( b )E.-I. Negishi, N.
Okukado, A. 0.King, D. E. Van Horn, and B. I. Spiegel, ibid., 1978,100,2254;( c )N. Okukado and
E.-I. Negishi, Tetrahedron Letters, 1978, 2357.
238 S. Yamagiwa, N. Hoshi, H. Sato, H. Kosugi, and H. Uda, J.C.S. Perkin I, 1978, 214.
239 0. H. Oldenziel, D. van Leusen, and A. M. van Leusen, J. Org. Chem., 1977,42, 3114.
R. H. Wollenberg, K. F. Albizati, and R. Peries, J. Amer. Chem. SOC.,1977, 99, 7365.
241 P. Savignac, M. Snoussi, and P. Coutrot, ( a ) Synth. Comm., 1978, 8, 19; (6) Synthesis, 1978, 133;
L. Lombard0 and R. J. K. Taylor, (c) ibid., 1978, 131; ( d ) Synrh. Comm., 1978,8,463.
242 M. P. Doyle, S. B. Williams, and C. C. McOsker, Synthesis, 1977, 717.
243
Borate esters have recently been prepared in quantitative yields by reaction of alcohols [e.g.
(-)-menthol] with BH3,SMez. See C. A.. Brown and S. Krishnamurthy, J. Org. Chem., 1978, 43,
273 1.
244 J. Tsuji, T . Yamakawa, M. Kaito, and T. Mandai, Tetrahedron Letters, 1978, 2075.
B. W. S. Kolthammer, P. Legzdins, and D. T . Martin, Tetrahedron Letters, 1978, 323.
* One questions the necessity for the rapid communication of the results in ref. 241d when they largely
represent a minor modification of the authors’ earlier work with the corresponding trimethylsilyl
in addition, some 20% of the paper is devoted to a discussion and comparison of the synthetic
methods used (ref. 241b, and refs. 241c, 241d) to prepare (Et0)2P(O)CH2C02H. A perfectly accept-
able published procedure exists for the preparation of the latter by hydrolysis of the corresponding ethyl
ester, which is commercially available. In this Reporter’s opinion such proliferation of the literature is to
be discouraged.
Monoterpenoids 23
In the area of functional group protection, pyridinium toluene-p-sulphonate

(PTPS)is the catalyst of choice for the almost quantitative tetrahydropyranylation
of alcohols [e.g. geraniol (99"/0),linalool (94%)] even in the presence of other
acid-sensitive functional groups (e.g. acetals, epoxides); PTPS-catalysed hy-
drolysis is also virtually quantitative [e.g. geraniol (loo%), linalool (99"/0)].'"~
Primary (e.g. geraniol) and secondary alcohols may be protected as 2-tetrahydro-
thienyl ethers formed almost quantitatively by reaction with 2-tetrahydrothienyl
diphenylacetate catalysed by toluene-p -sulphonic acid; cleavage with HgC12
(facile), HgC12-CaC03, AgN03-2,6-lutidine, and aqueous HOAc, but not
MeOH, suggests selective deprotection in the presence of other commonly used
protecting groups.247The use of t-butoxymethyl ethers (deprotection with
aqueous CF,C02H) for protecting primary (e.g. geraniol, citronellol) and secon-
dary alcohols has also been Benzeneseleninic anhydride has been
used to advantage to regenerate aldehydes and ketones (e.g. fenchone) from
1,3-dithiolans and 1,3-dithian~,'"~a process also reported (e.g. menthone 1,3-
dithiolan) to occur by photochemical irradiation in oxygen.25o
Further details of phase-transfer addition of dibromocarbene to a,@-
unsaturated esters and ketones [e.g. (18)]251and subsequent reductive monode-
bromination with tributyltin hydride (Vyl. 7, p. 34) have been p~blished;"~ Julia
the use of solid NaOH-Et,NCH,Ph C1- for the solid-liquid phase-
transfer catalytic generation of dichlorocarbene (addition to a -pinene and
limonene). Dichlorocarbene also provides a mild and efficient method for the
Beckmann fragmentation of anti-a-hydroxy-ketoximes into aldehydes (or
ketones) and nitriles [e.g. 2-exo- hydroxy-3-hydroxyiminobornaneinto (24; X =
CHO, Y = CN)].254Trimethylsilylcyclopropanes are synthesized by adding the
ylide Me3SiCH=SMe2, generated from methylthiomethyltrimethylsilane

methiodide and Bu"Li, to a,@-unsaturatedketones [e.g. ( 18)].255
246 M. Miyashita, A. Yoshikoshi, and P. A. Grieco, J. Org. Chem., 1977, 42, 3772; for another
application of this catalyst, see ref. 262.
247 C. G. Kruse, E. K. Poels, F. L. Jonkers, and A. van der Gen, J. Org. Chem., 1978, 43, 3548; high
selectivity for primary over tertiary alcohols is observed. The suggestion that similar reagents should
be standard for the THF- and THP-protection of alcohols must be questioned in the light of the
(unacknowledged) work reported in ref. 246.
248 H. W. Pinnick and N. H. Lajis, J. Org. Chem., 1978, 43, 3964.
249
D. H. R. Barton, N. J. Cussans, and S. V. Ley, J.C.S. Chem. Comm., 1977,751.
250 T. T. Takahashi, C. Y. Nakamura, and J. Y. Satoh, J.C.S. Chem. Comm., 1977,680.
251 L. K. Sydnes, Actu Chem. Scund., 1977, B31,823.
252 L. K. Sydnes, Actu Chem. Scund., 1978, B32,47.
253 S. Julia and A. Ginebreda, Synthesis, 1977, 682.
254 J. N. Shah, Y. P. Mehta, and G. M. Shah, J. Org. Chem., 1978,43,2078.
255 F. Cooke, P. Magnus, and G. L. Bundy, J.C.S. Chem. Comm., 1978,714.
Further papers of general synthetic interest include the full paper on the
UO,Cl,-MeOH-catalysed photoreactions of enones (Vol. 7, p. 8),256chlorination
of alcohols (e.g. menthol; poor yield) using C U C ~ , - P P ~ ~the ’ of 5,5-
, ~ ~use
dibromo-2,2-dimethyl-4,6-dioxo-1,3-dioxan for monobromination of saturated
aldehydes and ketones in high yield as well as a$-unsaturated ketones [e.g.
pulegone (21)]regioselectively at the a’-carbon atom,258debromination of
a -bromo-ketones with Fe2(C0)9-DMF-H20 (e.g. 3 -endo- bromocamphor to
3-exo-de~teriocamphor),~~~ conversion of ketones (e.g. camphor) into thio-
ketones with the dimer of p-methoxyphenylthionophosphine sulphide,260 the
mild transfer-nitration of alcohols (e.g. the borneols), without inversion, using
N-nitrocollidinium tetrafluoroborate,261and the preparation of trimethylsilyl
ethers (e.g. from citronellol) using bistrimethylsilyl etherz6, catalysed by the
mildly acidic pyridinium toluene-p - ~ u l p h o n a t e . ~ ~ ~
4 Biogenesis, Occurrence, Chemotaxonomy, and Biological Activity

Poulter has reviewed the evidence supporting an ionization-condensation-
elimination mechanism (Vol. 8,p. 24)in the prenyl-transfer reaction.263
(R)-(+)-Methyl p-tolyl sulphoxidz (synthesized in 100% optical purity by
microbial oxidation of methyl p-tolyl sulphide using Mortierella isabellina) has
been used to synthesize (3R)-(-)-mevalonolactone in 17% optical yield via a
straightforward alkylation-sulphoxide removal sequence involving (R)-(+)-t-
butyl a- (p-t~lyl)sulphinylacetate.~~~
Biogenesis.-Evidence supporting the hypothesis that 3-hydroxy-3-ethyl-
glutarate and homomevalonate (or their metabolic equivalents) are intermediates
in the biosynthesis of juvenile hormones in Manduca sexta has been published.265
The solvolytic behaviour of geranyl pyrophosphate (to yield
geraniol :linalool/ 1:5 ) in the presence of Mg2+or Mn2’ 266 is consistent with the
view263that two bivalent cations are required biochemically to ionize allylic
pyrophosphates in initiating prenyl-transfer via an ionization-condensation-
elimination mechanism. The micro-organism Kluyveromyces lactis produces
linalool and citronellol, with the yield of the latter increased by feeding with
gerani01.’~~ Banthorpe has pointed out that interpretation of the results of feeding
256 T. Sato, S. Yoshiie, T. Imamura, K. Hasegawa, M. Miyahara, S. Yamamura, and 0. Ito, Buff. Chem.
SOC.Japan, 1977, 50, 2714; for data on TiC14-MeOH photoreactions, see also Vol. 7, p. 33.
257 S. Miyano, H. Watanabe, H. Ushiyama, Y. Yamada, and H. Hashimoto, Nippon Kagaku Kaishi,
1978, 138.
258 R. Bloch, Synthesis, 1978,140; for pulegone bromination, the previously reported (Vol. 7, p. 8) enol
silyl ether route is more efficient.
259 R. Noyori, Y. Hayakawa, H. Takaya, S. Murai, R. Kobayashi, and N. Sonoda, J. Amer. Chem. SOC.,
1978, 100, 1759; see also ref. 566.
260 B. S. Pedersen, S. Scheibye, N. H. Nilsson, and S . - 0 . Lawesson, Buff.SOC.chim. befges, 1978,87,
223; the structural formula for thiocamphor is incorrect.
261 G. A. Olah, S. C. Narang, R. L. Pearson, and C. A. Cupas, Synthesis, 1978,452.
262 H. W. Pinnick, B. S. Bal, and N. H. Lajis, Tetrahedron Letters, 1978, 4261.
263 C. D. Poulter and H. C. Rilling, Accounts Chem. Res., 1978,11, 307.
264 E. Abushanab, D. Reed, F. Suzuki, and C. J. Sih, Tetrahedron Letters, 1978, 3415.
265 ( a ) F. C. Baker and D. A. Schooley, J.C.S. Chem. Comm., 1978,292; ( b ) E. Lee, D. A. Schooley,
M. S. Hall, and K. J. Judy, ibid., 1978, 290.
266 D. N. Brems and H. C. Rilling, J. Amer. Chem. SOC., 1977, 99, 8351.
267 F. Drawert and H. Barton, J. Agric. Food Chem., 1978, 2 6 , 7 6 5 .
Monoterpenoids 25
experiments may be complicated by seasonally dependent perturbations of

biosynthetic pathways in higher plants (see also Vol. 8, p. 14).268In further
experiments (see Vol. 8, p. 18)to elucidate the metabolic conversion of MVA into
(+)-thuj-3-one in Tanacetum vulgare,268*269 evidence favours the sequence
geraniol -+nerol -+cyclic monoterpenoids, geraniol being converted into nerol,
without the intermediacy of linalool, in a redox process. Using (3RS)-[5-
3H2]MVA, {(3R,4R)-[4- 3H1]MVA+ (3S,4S)- [4- 3H1]MVA}, or {(3R,4S)-[4-
3H1]MVA + (3S,4R)-[4-3Hl]MVA} in admixture with (3RS)-[2-14C]MVA, it
was shown that only the pro-(4R) hydrogen of MVA is incorporated into
(+)-thuj-3-one (in vivo),and into geraniol and nerol using cell-free extracts which
also incorporate both tritium atoms from [5-3H2]MVAinto geraniol but only one
into nerol; in vivo, only one tritium atom was incorporated from [5-3H2]MVA
into (+)-fhuj-3-0ne.’~~ A second paper268provides further evidence with in vivo
winter feeding experiments using (1R)- and (1S)-[l-3Hl]geraniol, and (1R)- and
(1S)-[l-3Hl]nerol, when it was shown that geraniol suffers stereospecific loss of
the pro- (1S )- hydrogen atom on conversion into nerol which suffers no hydrogen
loss at C-1 on further conversion into (+)-thuj-3-one. Non-winter feeding
experiments in Tanacetum vulgare, and feeding experiments in Pinus pinaster (a-
and p- pinenes), Menthu piperita and Eucalyptus globulus (1&cineole), and
Mentha spicata [carvone (18)],suggest that the straightforward redox conversion,
geraniol + nerol, may be perturbed by a nerol + geraniol interconversion
and/or C - 0 bond fission of pyrophosphate esters.268Some preliminary results
on using tissue cultures of Tunacetum cinerariifolium for examining pyrethrin
biosynthesis have been rep~rted.’’~Inouye has published furthur details of
iridoid biosynthesis in Lamium amplexicaule, Deutzia crenata, and Galium
spurium. Previously reported (and uncited - see Vol. 8, pp. 16, 17) data and the
results of additional feeding experiments with [2-14C]MVA, 1l-[10-3H]hy-
droxyiridodial glucoside, and 7-[ 10-3H]deoxyloganic acid are consistent with his
previous postulate (Vol. 8, pp. 16, 17) that the biosynthesis of asperuloside,
deutzioside, ipolamiide, lamiide, lamioside, and scabroside may involve the
biosynthetic sequence MVA ++ 10-hydroxygeraniol (or 1O-hydroxy-
nerol) ++ iridodial (via 10-oxoneral ?) + iridodial glucoside, followed by
further oxidative functionalization which may involve the oxidative sequence
CH3 + CHZOH + C 0 2 R at C-1 1 but not the reverse reductive processes.271
Feeding experiments with Thymus vulgaris suggest that thymol may be biosyn-
thesized by the aromatization of y-terpinene to p -cymene and subsequent
hydr~xylation.~~’ Using cell suspensions from Mentha strains, pulegone ( 21)has
been biotransformed into i s ~ m e n t h o n e . ’ ~Bornyl
~ pyrophosphate has been
shown to be an intermediate in the biosynthesis of borneol from NPP using a
Salvia officinalis enzyme preparation.274
268 D. V. Banthorpe, B. M. Modawi, I. Poots, and M. G . Rowan, Phytochemistry, 1978,17, 115.

269 D. V. Banthorpe, 0. Ekundayo, and M. G. Rowan, Phytochemistry, 1978,17, 1111.
270 M. M. Cashyap, J. S. H. Kueh, I. A . Mackenzie, and G. Pattenden, Phytochemistry, 1978,17, 544.
27 1
H. Inouye, S. Ueda, and S. Uesato, Phytochernistry, 1977,16, 1669.
272 A. J. Poulose and R. Croteau, Arch. Biochem. Biophys., 1978, 187, 307.
273 D. Aviv and E. Galun, Planta Med., 1978, 33, 70.
274
R. Croteau and F. Karp, Arch. Biochem. Biophys., 1977,184,77; for earlier work, see Vol. 8, p. 18.
Papers on the biosynthesis of monoterpenoid alkaloids lie outside the scope of

this Report.
Chemical communication in pine bark beetles has been reviewed;275related
papers of interest include the inhibition of aggregation of Ips pini by ( S ) - ( - ) -
ipsen01~’~ and an examination of species-specific response differences of Ips
species to ipsdienol e n a n t i o m e r ~ The
. ~ ~ ~oviposition behaviour of the house
longhorn beetle (Hylotrupes bajulus) is pheromone-stimulated by (-)-verbenone
and synergized by p -cyrnen-8-01.~~’ Neral and/or geranial are components of the
sex pheromone of the parasitic wasp (Itoplectis ~ o n q u i s i t o r )The
.~~~mosquito
(Aedes aegypti) larvicide present in Tagetes minuta has been shown to be
(5E)-0cimenone (25).”’
Essential Oils and Chemotaxonomy.-This section reviews the literature of the

past year for essential oil analyses, but covers the past two years (see Vol. 8, p. 19)
for phytochemical papers reporting variation of monoterpenoid content accord-
ing to geographical, seasonal, and environmental factors, taxonomic and evolu-
tionary implications, hybridization, and genetics of terpenoid development. For
the previous report on Chemotaxonomy, see Vol. 7, p. 222.
Further papers in a series on recent progress in essential oils have been
published.2i0d
Essential oil composition studies of interest concern Mentha rotundifolia
[-85% piperitenone epoxide (26)],281Artemisia afra (cineole, artemisia ketone,
275 M. C. Birch, Amer. Scientist, 1978, 66, 409.

276 M. C. Birch, D. M. Light, and K. Mori, Nature, 1977, 270,738.
277 J. P. Vitt, G. Ohloff, and R. F. Billings, Nature, 1978, 272, 817.
278 M. D. Higgs and D. A . Evans, Experientia, 1978, 34,46.
279 D. C. Robacker and L. B. Hendry, J. Chem. Ecol., 1977,3, 563.
A . Maradufu, R. Lubega, and F. Dorn, Lloydia, 1978, 41, 181.
280a Recent reviews are B. M. Lawrence, Perfumer and Flavorist, 1978, 2(7), 44; 1978,3(2), 45; 1978,
3(3),46. For earlier reviews in this series, see B. M. Lawrence, ‘Essential Oils 1976-1977’, Allured
Publishing Corp., Wheaton, Illinois, 1978.
281 S.4.Fujita, T. Nakano, and Y. Fujita, Nippon Nogei Kagaku Kaishi, 1977, 51, 699; an earlier
analysis, R. H. Reitsema, J. Amer. Chem. Soc., 1956,78, 5022, reports significantly less (26).
Monoterpenoids 27
artemisia Chenopodium ambrosioides ( a ~ c a r i d o l e )and

, ~ ~ ~Cymbo-
pogon winterianus (Burmese type) (citronellal, c i t r ~ n e l l o l )Two
.~~~ papers report,
as natural products, trace amounts of karahanaenol(Z7; X = H,OH) in Cupressus
s e m p e r v i r e n ~and
~ ~ ~/3 -pinene epoxide in Picea abies ;286 a third reports the
presence of (+)-cis-sabinene hydrate (28) in a new chemical strain of Mentha
candi~ans.~~’
Many papers report monoterpenoid analyses with geographical and seasonal

variations. Geographical variations have been reported for Abies amabilis288and
A. g r a n d i ~ Pinus
, ~ ~ ~~ o n t o r t a and
, ~ ~ Satureja
~ d o ~ g l a s i i Five
. ~ ~ ~compositional
types were identified for S. douglasii (cf. Vol. 7, p. 223)291nalthough environ-
mental conditions, e.g. moisture stress, temperature, light, were also shown to
influence monoterpenoid yield and composition.29’b~cThe effect of moisture
stress on Pinus taeda has been and data on geographical monoter-
penoid variations in Pinus p o n d e r ~ s aslash , ~ ~ pine,294
~ and the Sitka spruce (Picea
itche ens is)^^^ have appeared. Seasonal variations in the monoterpenoid content of
essential oils from Salvia ~ c l a r e a Mentha ~ ~ gentilis [( 1R,4S)-
, ~ ~ ~ j a p o n i ~ a , ’M.
(+)-4-hydroxyisomenthone (29) is a minor and a second
chemotype of M. g e n t i l i ~have ~ ~ been
~ ~ reported.
Further papers on new chemotypes include reports of two chemotypes of
Achillea ageratum (one high in artemisia ketone and artemisyl acetate content
J. Garnero, Parfums, Cosmet., Aromes, 1977, 16, 45; Chem. Abs., 1978, 88, 11 725 incorrectly
assigns this work to M. Gavarry.
283 G. S . Gupta and M. Behari, Indian Perfum., 1975, 18(2), 40; the delay between publication and
abstracting (Chem. Abs., 1977,87, 122 623) is to be deplored.
’“ B. L. Kaul, D. K. Choudhary, and C. K. Atal, Indian J. Pharm., 1977, 39,42.
J. Garnero, P. Buil, D. Joulain, and R. Tabacchi, Riuista Ital. Essenze-Profumi, Piante OfJic.,Aromi,
Saponi, Cosmet., Aerosol., 1978,60,99.
286 V. Heemann and W. Francke, Planta Med., 1977,32,342.
287 D. Karasawa and S. Shimizu, Agric. and Biol. Chem. (Japan), 1978,42,433;the major component
(85%) is (+)-trans-sabinene hydrate.
E. von Rudloff and R. S. Hunt, Canad. J. Bot., 1977,55, 3087.
D. J. Houkal, Diss. Abs. Internat. ( B ) , 1976, 37, 2592; see also Vol. 7, p. 222.
290 G. I. Forrest, Comm. Eur. Communities, Rep. EUR, 1977, EUR 5885, p. 55 (Chem. Abs., 1978,88,
86 175).
291 D. E. Lincoln and J. H. Langenheim, Biochem. System. Ecol., ( a ) 1976, 4, 237; ( 6 ) 1978, 6, 21;
(c) J. Gershenzon, D. E. Lincoln, and J. H. Langenheim, ibid., 1978,6,33.
’” A. R. Gilmore, J. Chem. Ecol., 1977,3,667.
293 R. H. Smith, U.S. Dee. Agric., Tech. Bull., 1977, 1532, 1 (Chem. A b s , 1977, 87, 98798).
294 C. R. Gansel and A. E. Squillace, Siluae Genet., 1976,25, 150; Chem. Abs., 1978,88,60 112 does
not record the botanical name of this species.
295 E. M. von Rudloff, Phytochemistry, 1978, 17, 127.
296 T. Yoshida and T. Sawasaki, Nettai Nogyo, 1978, 21, 145 (Chem. Abs., 1978,89, 94 876).
297 S.-I. Fujita, T. Nakano, and Y. Fujita, Nippon Nogei Kagaku Kaishi, 1977, 51,405.
298 K. Umemoto and T. Nagasawa, Nippon NogeiKagaku Kaishi, ( a ) 1977,51,659;( b ) 1978,52,191.
and the other high in 1,8-cineole content),299a new strain of Chenopodium

ambrosioides [high (-)-pinocarve01 (30) content],300 and a chemotype of Pinus
ponderosa which may prove to be resistant to the pine beetle Dendroctonus

brevicomis because of its high limonene content.293A number of papers report
studies on hybrids of Mentha species.3o1From a clone study of Picea d i e s , it has
been suggested that the regulation of monoterpenoid biosynthesis (to high
car-3-ene/terpinolene content, or to high limonenelp-phellandrene/pinene
content) is controlled by a dominant-recessive allele pair of a single gene locus3o2
analogous to the genetic control of car-3-ene production in Pinus s y l ~ e s t r i s . ~ ~ ~
Pyrethroids and Related 1nsecticides.-A book of reviews was omitted from
earlier The limited space available for this Report restricts the
discussion of this year's pyrethroid literature.305
Papers of analytical interest include the g.c.-m.s. analysis of the six naturally
' ~ resolution307" and optical purity determination of
occurring p y r e t h r i n ~ , ~g.c.
~ ~ (' * ) - a l l e t h r ~ I o n e(a
synthetic allethronyl c h r y s a n t h e m a f e ~ ~and ~ ~synthesis
~~ of
which has been published308),and h.p.1.c. analysis of the six naturally occurring
299 R. Grandi, W. Messerotti, and U. M. Pagnoni, Phytochemistry, 1976, 15, 1770.

30" K. Umemoto, Nippon Nogei Kagaku Kaishi, 1978, 52,149.
301 ( a )A. G. Nikolaev, A. V. Dizdar, E. M. Pelyakh, Yu. S. Popov, and L. N. Chelovskaya, Izuest. Akad.
NaukMold. S.S.R., Ser. biol. khim. Nauk, 1977, (6), 16 (Chem. Abs., 1978,88,166 844); ( b ) E. M.
Pelyakh, V. I. Chobanu, A. G. Nikolaev, and Q. Z. Nguyen, ibid., 1976, (6), 16 (Chem. A h . , 1977,
86, 168 016); ( c ) A. G. Nikolaev, VIIth International Congress of Essential Oils, Kyoto, 7-11th
October, 1977, Abstract No. 19 (Riuista Ital. Essenze-Profumi, Piante Ofic., Aromi, Saponi,
Cosmet., Aerosol., 1978, 60, 131); ( d ) T . Sacco and M. Gallino, Atti-Conv. Naz. Olli Essenz. Sui
Deriv. Agrum., 1976,8-9, 82 (Chem. Abs., 1978,88,41 533).
302 I. Esteban, F. Bergmann, H. R. Gregorius, and 0. Huhtinen, Silvae Genet., 1977, 25, 59 (Chem.
Abs., 1978,88,60 213).
303 R. Hiltunen, Ann. Acad. Sci. Fennicae, Ser. A#, 1976, 208, 1 (Chern. Abs., 1978,88, 86 184);see
also Vol. 7, p. 224.
304 'Pyrethrum Flowers', ed. R. H. Nelson, 3rd edn., McLaughlin Gormley King Co., Minneapolis,
U.S.A., 1975.
305
Fortunately the keyword search for pyrethroids is relatively efficient and a significant proportion of
this year's literature may be found in only two journals, viz. J. Agric. Food Chem. and Pesticide Sci.
3"6 R. L. Holmstead and D. M. Soderlund, J. Assoc. Ofic. Analyt. Chemists, 1977, 60, 685.
307 M. Horiba, H. Kitahara, and A. Murano, Agric. and Biol. Chem. (Japan), ( a ) 1978, 42, 671; ( 6 )
1977,41, 2003.
308 G. Piancatelli, A. Scettri, G. David, and M. D'Auria, Tetrahedron, 1978, 34, 2775.
Monoterpenoids 29
pyrethrin~~ and
' ~ of permethrin310 and some cyano-substituted The
most active form of one of the latter (cypermethrin) has been shown to have the
same S-configuration at the a -cyanobenzyl carbon atom312as that observed for
decamethrin (Vol. 5, p. 16) and analogues.311Synthetic activity has been directed
towards the synthesis of (lR)-cis-and (1R)-trans-permethrin labelled with 14Cat
C-2 of the substituted vinyl group,313of permethrin metabolites314 and cyano-
substituted analogues,311of methyl-substituted cyclohexenylmethyl and cyclo-
hexadienylmethyl c h r y ~ a n t h e m a t e s of, ~ ~pyrethrolone
~ and of
substituted indanyl c h r y s a n t h e m a t e ~Pyrethroid
.~~~ degradation studies include
the photochemical decomposition of d e ~ a m e t h r i n ,~~ e' ~r m e f h r i nand
, ~ ~kadeth-
~
rin320and the degradation of labelled321"and ~ n l a b e l l e dpermethrin
~~l~ in soil, on
cotton leaves,322 in bean and in hens322band of cypermethrin in
soi1.321 b.323 Other papers of interest concern decamethrin metabolism in
permethrin metabolism in lactating cows,325and a discussion of structural and
biological links between pyrethroids and DDT in new Structure-
toxicity relationships and degradation of toxaphene components have also been
5 Acyclic Monoterpenoids
Terpenoid Synthesis from Isoprene.-Some prenylation procedures have been
reported An efficient conversion of prenyl into prenyl
acetate329has been described and the synthon (31; X = OH) (Vol. 7, p. 10) has
309 D. Mourot, J. Boisseau, and G. Gayot, Analyt. Chim. A c f a , 1978, 97, 191.
310 S. Lam and E. Grushka, ( a )J. Chromatog. Sci., 1977,15,234;( b )J. Chromatog., 1978,154,318; ( c )
E. J. Kikta, jun. and J. P. Shierling, ibid., 1978, 150, 229.
3 1 1 M. Elliott, N. F. Janes, D. A. Pulman, and D. M. Soderlund, Pesticide Sci., 1978, 9, 105. For an
investigation of insecticidal activity, see M. Elliott, A. W. Farnham, N. F. Janes, and D. M.
Soderlund, ibid., 1978, 9, 112.
312 K.-I. Aketa, N. Ohno, N. Itaya, I. Nakayama, and H. Yoshioka, Agric. and Biol. Chem. (Japan),
1978,42,895.
3 1 3 I. Nakatsuka, F. Shono, and A. Yoshitake, J. Labelled Compounds, 1977, 13, 561.
314 T. Unai and J. E. Casida, J. Agric. Food Chem., 1977,25, 979.
"' F. Sugawara, T. Sugiyama, A. Kobayashi, and K. Yamashita, Agric. and Biol. Chem. (Japan), 1978,
42, 847.
316 K. Okada, M. Nozaki, Y. Takashima, N. Nakatani, Y. Nakatani, and M. Matsui, Agric. and Biol.
Chem. (Japan), 1977,41,2205.

317 Y. Nakada, S. Muramatsu, M. Asai, S. Ohno, and Y. Yura, Agric. and Biol. Chem. (Japan), 1978,42,
1357; Y. Nakada, S. Ohno, M. Yoshimoto, and Y. Yura, ibid., p. 1365.
318 L. 0. Ruzo, R. L. Holmstead, and J. E. Casida, J. Agric. Food Chem., 1977, 25, 1385.
319 R. L. Holmstead, J. E. Casida, L. 0. Ruzo, and D. G. Fullmer, J. Agric. Food Chem., 1978,26,590.
320 K. Ohsawa and J. E. Casida, 175th A.C.S. Meeting, Annaheim, California, March 1978, Abstracts
PEST, No. 53.
321 D. D. Kaufman, E. G. Jordan, and A. J. Kayser, 175th A.C.S. Meeting, Annaheim, California,
March 1978, ( a ) Abstracts PEST, No. 48; ( b ) Abstracts PEST, No. 47.
322 L. C. Gaughan and J. E. Casida, ( a )J. Agric. Food Chem., 1978,26,525;( b ) 175th A.C.S. Meeting,
Annaheim, California, March 1978, Abstracts PEST, No. 7.
323 T. R. Roberts and M. E. Standen, Pesticide Sci., 1977,8, 305.
324 L. 0. Ruzo, T. Unai, and J. E. Casida, J. Agric. Food Chem., 1978, 26, 918.
325 L. C. Gaughan, M. E. Ackerman, T. Unai, and J. E. Casida, J. Agric. Food Chem., 1978,26,613.
326 G. Holan, D. F. O'Keefe, C. Virgona, and R. Walser, Nature, 1978, 272, 734.
327 M. A. Saleh, W. V. Turner, and J. E. Casida, Science, 1977,198,1256;W. V. Turner, J. L. Engel, and
J. E. Casida, J. Agric. Food Chem., 1977,25,1394;M. A. Saleh and J. E. Casida, ibid., 1978,26,583.
328 For an industrial synthesis from isoprene, see J. Levy and N. J. Christensen, U.S. P. 4 036 899 (Chem.
Abs., 1977,87, 117 5 5 8 ) .
329 J. Horino, K. Moriguchi, and Y. Mitsuta, Jap. P. 95 606/1977 (Chem. Abs., 1978,88, 37 269).
been converted into the useful synthons (32) and (33).330The 2-isomer of (32)
results from the stereoselective S02C12-inducedrearrangement of (3 1; X = OH)
to the corresponding 2-8-chlorosulphone, followed by hydrolysis, whereas E-
(32) is obtained uia an oxidation-allylic transposition Pummerer
PhS&
X
rearrangement of (31; X = OAc) followed by a [1,2] shift yields (34) which after
hydrolysis undergoes photochemical [1,3] migration to yield (33).3306 y -
Acetoxytiglicaldehyde is also readily available from (34).3306Julia and co-
workers have reported (35; X = SMe or SPh),33’ (36),331Q(37; X = Y = SMe or
SPh),33’band (38)3316as further useful synthons.
PhS+
PhSO
Ethyl geranate has been prepared stereoselectively under phase-transfer

conditions by prenylation of ethyl E-3-methyl-4-benzenesulphonylbut-2-enoate
and d e s ~ l p h u r i z a t i o nBiomimetic
.~~~ synthesis of (39) from dimethylallyl acetate
and isopentenyl acetate (1:3) catalysed by LiC104-AcOH has been examined;333
:Iy:
the corresponding alcohol (40) is obtained efficiently from isopentenyl acetate by
QOAc OAc
reaction with an excess of 2-methylbut-3-en-2-01, catalysed by trifluoroacetic

Base-catalysed reaction of prenyl chloride with 3-methylbut-2-enonitrile
330 P. J. R. Nederlof, M. J. Moolenaar, E. R. de Waard, and H. 0.Huisman, Tetrahedron,( a ) 1978,34,

447; ( b ) 1978,34,2205. For another synthesis of y-acetoxytiglicaldehyde, via nitroacetoxylation of
isoprene, see P. A. Wehrli and B. Schaer, Synthesis, 1977,649.
331 ( a )V. Ratovelomanana and S. Julia, Synth. Comm., 1978, 8, 87; ( b ) J.-C. Clinet and S. Julia, J.
Chem. Res. ( S ) , 1978, 125. See also ref. 366.
332 G. Cardillo, M. Contento, M. Panunzio, and A. Umani-Ronchi, Chem. and Ind., 1977, 873.
333 M. Julia, C. Perez, and L. Saussine, J. Chem. Res. ( S ) , 1978, 268.
334 M. Julia and L. Saussine, J. Chem. Res. ( S ) , 1978, 269.
Monoterpenoids 31
produces a lavandulyl carbon Miginiac et ~ 1have. been

~ unable
~ ~to
reproduce results reported previously (Vol. 7, p. 10) for the [(q5-C5H5),TiC12]-
catalysed addition of allylic Grignard reagents to isoprene337 and subsquent
reaction with carbon dioxide or carbonyl compounds, in that allylic transposition
accompanies the latter; further investigation seems warranted. The structure of
the tail-to-tail isoprene-magnesium 2 : 1 adduct has been shown to be a 27-
membered m a c ~ o c y c l e . ~ ~ ~
Telomerization of isoprene using lithium and substituted dialkylamines (e.g.
di-isopropylamine) yields (41) in addition to m ~ r c e n e Further
. ~ ~ ~ details have
been published on the effects of water (cf. Vol. 8, p. 21) and amine structure (cf.
Vol. 7, p. 11) on the [NiC1,(PPh3),]-NaBH4-catalyseddimerization of iso-
~ r e n e . Regioselective
~~' head-to-head dimerization of isoprene occurs with, e.g.,
(FMePhSi), in the presence of [(PPh3),PdCl2] or [Pd(PPh3),] (cf. Vol. 7, p. 11),341
in contrast to a further report (Vol. 8, p. 20) of solvent-dependent predominant
tail-to-tail dimerization {Pd[(Ph2PCH,),],-C0,} to (42),342nmonohydration of
which is reported via diene protection with sulphur Compound (43)
is the major product of thermal decomposition of bis-(3,3-dimethylallyl)zinc,

together with irregular monoterpenoid d i e n e ~ an
; ~almost
~ ~ identical product
ratio results from CrCl3-LiA1H4-THF reductive dimerization of prenyl
bromide.344Isoprene (in propylene carbonate) is cyclodimerized to limonene by
the electrochemically generated [Fe(N0)2],345 and oxidized anodically in
methanol to a complex mixture of methoxylated dimers and t r i r n e r ~ Hy-.~~~
droxycitronellol has been synthesized via CuC1-catalysed coupling of 4-acetoxy-
1-chloro-2-methylbut-2-ene and 2-methylbut-3 -yn-2-01.~~~
Some further syntheses with C5units are discussed in the next section.
335 T. Miyakoshi, H. Omichi, and S . Saito, Nippon Kagaku Kaishi, 1978,1176.
336 ( a ) F. Barbot and Ph. Miginiac, J. Organometallic Chem., 1978,145,269.
337
For a full discussion of the non-catalysed addition of 3-methylbut-2-enylmagnesiumchloride to
isoprene, see H. Lehmkuhl, D. Reinehr, K. Mehler, G. Schomburg, H. Kotter, D . Henneberg, and
G. Schroth, Annalen, 1978,1449.
338 H. Yasuda, Y. Nakano, K. Natsukawa, and H. Tani, Macromolecules, 1978,11,586.
339 A. Murata, S. Tsuchiya, A. Konno, and H. Ikeda, Jap. P. 23 906/1978 (Chem. Abs., 1978,89,
42 395).
340 I. Mochida, K. Kitagawa, H. Fujitsu, and K. Takeshita, J. Catalysis, 1978,54,175.
341 K.Tamao, S. Okazaki, and M. Kumada, J. Organometallic Chem., 1978,146,87.
342 ( a )Y.Inoue, S . Sekiya, Y. Sasaki, and H. Hashimoto, J. Synth. Org. Chem.,Japan, 1978,36,328;
(b)
P. A. Ochsner, U.S. P. 4 066 710 (Chem. Abs., 1978,88,105 610).
343 R. Benn, E. G. Hoffmann, H. Lehmkuhl, and H. Nehl, J. Organometallic Chem., 1976,146,103.
344 Y. Okude, T. Hiyama, and H. Nozaki, Tetrahedron Letters, 1977,3829.
345 E.Le Roy, F. Petit, J. Hennion, and J. Nicole, Tetrahedron Letters, 1978,2403.
346 H. Baltes, E. Steckhan, a n d H . J. Schafer, Chem. Ber., 1978,111,1294.
347 R.E.Close and J. M. Derfer, U.S. P. 4 056 573 (Chem. Abs., 1978,88,51 041).
2,6-Dimethyloctanes.-The lack of recent references (only one post- 1963) in a

review of 7-hydroxycitronellal is to be deplored (cf.Vol. 3, p. 45;Vol. 5 , p. 14;
Vol. 8, p. 25).348
The diol (44)has been isolated from Greek tobacco (cf. Vol. 8, p. 26) and
synthesized in low yield by S e 0 2 allylic oxidation of l i n a l o 0 1 ; ~(44)
~ ~ (chirality
OH
(44)
unspecified) and the corresponding 2-isomer are also present as primary p-D-
glucosides (betulalbuside A and B respectively) in Betula alba and Chaenomeles
j a p o n i ~ a . ~3,7-Dimethylocta-1,6-diene-3,4-diol
~' ('cornusol') is a component of
Cornus c o n t r o ~ e r s aand
, ~ ~citronellyldiethylamine
~ has been isolated from Pelar-
gonium gra veolens.3s2
The 'H n.m.r. spectra of isoprene and myrcene have been analysed in
and 'H n.m.r. data on a number of bisulphite adducts of citral and citronella1 have
been The existence of a steric interaction between an alkene double
bond and a heteroatom in a S-position (e.g. 6-bromo-7-hydroxy-3,7-dimethyl-
oct-2-ene, 7-bromo-6-hydroxy-2,6-dimethyloct-2-ene, 6,7-epoxy-3,7-
dimethyloct-2-ene) has been demonstrated from 13C n.m.r. data.3s5
(1R)- and (1S)-[l-3H,]geraniol and (1R)- and (1S)-[l-3Hl]nerol have been
synthesized.268 Treatment of the pyrrolidenecarbodithioate (45) with excess
(45)
methyl iodide in HMPA in the presence of LiC0,-LiF at room temperature
provides a mild and efficient procedure for the steroselective synthesis of the
all-trans allo-ocimene uia an S-methylation-elimination process.356Syntheses
have been of chiral citronellol, 7-methoxycitrone11o1, 7-methoxy-
348 G. T. Walker, Seifen, Ole, Fette, Wachse, 1977, 103, 432.
349 D. Behr, I. Wahlberg, T. Nishida, and C. R. Enzell, Acra Chem. Scand., 1978, B32,228.
350 R. Tschesche, F. Ciper, and E. Breitmaier, Chem. Ber., 1977, 110, 3111.
351 T. Kurihara and M. Kikuchi, J. Pharm. SOC.Japan, 1978,98, 969.
352 W. Rojahn and E. Klein, Dragoco Rep. (Ger. Edn.), 1977, 24, 150.
353 R.K. Harris and A. V. Cunliffe, Org. Magn. Resonance, 1 9 7 7 , 9 , 4 8 3 .
354 T. J. Johnson and R. A. Jones, Tetrahedron, 1978, 34, 547.
355 M. E. van Dommelen, L. J. M. van de Ven, H. M. Buck, and J. W. de Haan, Rec. Trau. chim., 1977,
96, 295.
356 T. Hayashi, A. Sakurai, and T. Oishi, Chem. Letters, 1977, 1483.
Monoterpenoids 33
citronellal, and citronellic acid of R or S configurations in high optical purity [e.g.

( R ) -(+)-7-methoxycitronellal, 99.5% enantiomeric purity] by known procedures
(for related work, see Vol. 8, pp. 25,26). The paper also reports that the [a12for
optically pure (R)-(+)-7-hydroxycitronellalshould be + 14.9" (CHCl,) (cf.Vol. 3,
p. 45, ref. 205).'s9b (R)-(+)-Menthocitronello1 (46) of high, but unspecified,
optical purity has been synthesized from the corresponding nitrile which is
obtained from (-)-menthone via Beckmann rearrangement followed by known
lactam cleavage using PC15.3s7Geraniol syntheses include cleavage of (47) with
Na,CO,-MeOH to yield methyl (E)-3-methyl-7-oxo-oct-2-enoate and straight-

forward elaboration via methyl g e ~ a n a t e , conversion
~'~ of 6-methylhept-5-en-l-
yne into the corresponding (E)-2-methylalkenylalane using Me3Al-C12ZrCp2
and reaction with formaldehyde via the derived ate and a straight-
forward conversion of N,N-dipropylgeranylamine (obtained from myrcene-
Pr2NH-BuLi; cf. Vol. 8, p. 23) via geranyl chloride obtained by treatment with
ethyl chlor~forrnate.~'~
Nerol was also obtained with high stereoselectivity using
the same reaction sequence on the isoprene telomerization product N,N-di-
alkylnerylamine. This is a better alternative to the less selective amine-oxide
rearrangement route (Vol. 5, p. 12; Vol. 7, p. 11).3s9The poor quality of the
Chemical Abstract hides details of the preparation of (48) via dimethylcyclo-
octene pyrolysis and hydrof~rmylation.~~'
Diels-Alder reaction of itaconic anhydride with cyclopentadiene yields the

adduct (49) which is converted into (50) (Scheme 1)for quantitative retro-Diels-
Alder thermolysis to racemic ipsenol (51),361reminiscent of the last steps of
Mori's ipsenol synthesis (Vol. 6, pp. 18, 19). Both ipsenol (51) and the cor-
357 K. Derdzinski and A. Zabza, Bull. Acad. polon. Sci., Se'r. Sci. chim., 1977, 25, 529.
358 K. Tsuzuki, H. Hashimoto, H. Shirahama, and T. Matsumoto, Chem. Letters, 1977, 1469.
359 K. Takabe, T. Katagiri, and J. Tanaka, Chem. Letters, 1977, 1025. For related work where
rearrangement occurs, see Vol. 4, p. 17. For the reverse conversion of geraniol to geranyl chloride
without rearrangement, see Vol. 3, p. 38, ref. 186.
360 A. J. De Jong, Ger. Offen. 2 704 547 (Chem. A h . , 1978, 88, 170 341); regrettably (48) has been
named dihydromyrcenol (cf. Vol. 3, p. 15).
361 J. Haslouin and F. Rouessac, Bull. SOC.chim. France, 1977, 1242.
(49) liv, v
A vii
t t
VI
(51)
Reagents: i, NaBH4-DMF; ii, B u ~ A I H-80
, "C; iii, Bu'MgBr; iv, C S H ~ N H C ~ O ~ C I - C H ~C~~,
0 "C;
V, BUbAlH, -80 "c;vi, Ph3PCH2-C&6, 8 0 "c;V i i , 4 5 0 "c
Scheme 1
responding ipsdienol have been synthesized by vinylcuprate addition to the

corresponding ketones [e.g. (52)] followed by reduction; (52) is readily available
by lithiation of allene and reaction with N,N-dimethyl-3-methylbut-2-
enamide.362The useful synthon (53; X = CHO), which is formed from the Claisen
rearrangement product (53; X = C0,Me) of buta-2,3-dienyl dimethyl
orthoacetate, provides short and efficient syntheses of ipsenol (51) and ips-
~ ~analogous known Claisen rearrangement of the but-2-enyl ortho-
d i e n 0 1 ; ~the
ester and conversion into a mixed anhydride is the basis for a synthesis of
(*)-dihydrotagetone (54) via acylation of trimethylsilyl lithio-i~ovalerate.~~~
[2,3] Sigmatropic rearrangement of ( 5 5 ) , which is formed by thiophilic

Grignard addition to the corresponding dithioester, followed by methylation and
hydrolysis, yields the dihydromyrcenone (56; 25% yield).365Julia et al. have used
the synthon (37; X = H, Y = PhSO) and a lithio-derivative of a protected cyan-
hydrin (cf. Vol. 8, p. 59) in a straightforward synthesis of the tagetones (57;
A d : 2 / 5 5 : 45).366
362
J. C. Cline?.and G. Linstrumelle, Nouueau J. Chim., 1 9 7 7 , 1 , 3 7 3 ; for a related synthon (38) see ref.
331b.
363
M. Bertrand and J. Viala, Tetrahedron Letters, 1978, 2575.
364
R. Coufignal and J.-L. Moreau, Tetrahedron Letters, 1978, 3713.
365
S. Masson, M. Saquet, and A. Thuillier, Tetrahedron, 1977, 33, 2949. Julia et al. reported a very
similar sigmatropic rearrangement some time ago; see S. Julia, V. Tatovelomanana, and C. Huynh,
Compt. rend., 1974, 218, C, 371 and Vol. 8, p. 32.
366
E. Guittet and S. Julia, Tetrahedron Letters, 1978, 1155.
Monoterpenoids 35
Another ortho-ester Claisen rearrangement involves rearrangement of 3 3 -

dimethylhexa-2,5-diene-l-y1diethyl orthoacetate followed by Cope rearrange-
ment in situ to yield ethyl 3,7-dimethylocta-3,7-dienoate(E :2/55 :45).367The
conversion of 6-methylhept-5-en-l-yne into the corresponding (El-2-methyl-
alkenylalane using Me,Al-Cl,ZrCp, has also been used in syntheses of ( E ) -
geranic acid and its ethyl The addition of dimethylallylcarbene to
isoprene and 2-methylbut-l-ene yields ( 5 8 ; R = vinyl or ethyl, respectively);
acid- and base-catalysed rearrangements of (58) may lead to regular and/or
irregular monoterpenoid carbon Sodium-liquid ammonia treat-
ment of (58; R = vinyl) yields the dihydromyrcene (59)whereas peracid oxidation
followed by treatment with methanolic HCl yields, e.g., (60).3686An interesting
stereospecific hydrogen migration has been reported following the observation
that N,N-diethylnerylamine and N,N-diethylgeranylamine rearrange to the
corresponding trans-enamine of citronella1 (6 1; up to 90Y0) using [HCo(N,)-
OM
(PPh3)3]or cobalt octanoate-PPh3-Et3Al as catalysts. With the former Ziegler-

type catalyst containing chiral (including monoterpenoid) phosphines or diphos-
phines, up to 33% enantiomeric excess of 3R-or 3S-citronella1 can be obtained,
enantioselectivity being both ligand- and temperature-dependent, and at the
expense of isolated yields.369
Other syntheses of interest concern citral (via acetal pyrolysis; cf. Vol. 6 , p. 14;
Vol. 7 , p. 15),370another report (Vol. 7, p. 17) of dehydrolinalool rearrangement
1,1,2-trifluorolinaloo1372and the related 7-
to ~ i t r a 1 1,2-difluorolinalo01,~~~
,~~~
367 Y. Fujita, T. Onishi, and T. Nishida, Synthesis, 1978,532.

368 L. Crombie, P. J. Maddocks, and G. Pattenden, Tetrahedron Letters, ( a ) 1978,3479; ( b ) 1978,3483.
369
H. Kumobayashi, S. Akutagawa, and S. Otsuka, J. Amer. Chem. SOC., 1978, 100, 3949; S.
Akutagawa and H. Kumobayashi, Jap. P. 77 005/1977 (Chem. Abs., 1977,87,201 817).
37" W. Leimgruber and D. H. Valentine, jun., U.S. P. 4 016 212 (Chem. Abs., 1977, 87, 136 042).
371 P. Chabardes and E. Kuntz, Ger. Offen. 2 657 335 (Chem. Abs., 1977,87, 136 056).
372 R. Sauvstre, D. Masure, C. Chuit, and J. F. Normant, Synthesis, 1978, 128.
methyl-3-trifluoromethylocta-1,6-dien-3-ol,373 (3RS,6R)-2,6-dimethyloct-7-
ene -2,3-diol ,374 and p -D-glucopyranosyl citronellyl phosphate. 375
Further work (Vol. 8, p. 26) has been published on geraniol and nerol
biotransformation using callus tissue from Cannabis ~ u t i v u The . ~ ~ micro-
~
biological transformation products of g e r a n i 0 1 , ~l ~i n~a~l o 0 1 , ~and
~ ~ ~ner01,'~~
using Pseudomonas incognita have been analysed and metabolic pathways
investigated.377b Geraniol and nerol metabolites may result from allylic C-3
methyl oxidation, C-2-C-3 dihydroxylation, and/or alcohol oxidation; linalool
metabolites result from hydroxylation at the C-3 methyl group or the formation of
(44).377bAttempts to mimic the formation of the chloroform-soluble (62)378failed
(62)
with a related phenolic diether analogue of monocarboxylic acid polyether
antibiotics.379
The cyclization of 3,7-dimethylocta-1,6-diene [to e.g. (63; X = Y = H)] using
Bu"Li-TMEDA may occur via the polar equivalent of the ene A
kinetic analysis of the thermal rearrangement of linalyl trimethylsilyl ether
confirms that the four diastereomeric products [ e . g (63; X = OSiMe,, Y = H)]
are each formed by distinct intramolecular ene reactions although it has been
impossible to specify whether the transition states are endo or ~ x o . Thermolysis
~'~
of dehydrolinalool to (64; X = OH) is a n a l o g o ~ s ; likewise
~~' with 3,7-dimethyl-
oct-6-en-1- ~ n e . ~ 'The
* full paper on the [2,3] sigmatropic rearrangement of
geranyl o -nitrophenyl selenoxide followed by o -nitrobenzene seleninic acid-
%
373 F. Camps, R. Canela, J. Coli, A. Messeguer, and A. Roca, Tetrahedron, 1978, 34, 2179.
374 G . J . Cernigliaro and P. J . Kocienski, J. Org. Chem., 1977, 42, 3622; this compound is named
incorrectly in this paper.
375 L. L. Danilov, L. V. Volkova, and R. P. Evstigneeva, J. Gen. Chem. (U.S.S.R.),1977,47, 1948.
376 H. Itokawa, K. Takeya, and S . Mihashi, Chem. and Pharm. Bull. (Japan),1977,25,1941;K. Takeya
and H. Itokawa, ibid., p. 1947.
377 J. Rama Devi and P. K. Bhattacharyya, Indian J. Biochem. Biophys., ( a ) 1977, 14, 288; ( 6 ) ibid.,
p. 359. For earlier linalool metabolic work with Pseudomonas, see Vol. 3, p. 10.
378 The formation of (62) by exposing the corresponding geranyl acetate oxidation product to potassium
ion was inadvertently omitted from a previous Report, R. E. Hackler, J. Org. Chem., 1975,40,2978.
379 J. 0. Gardner and C. C . Beard, J. Medicin. Chem., 1978, 21,357.
38" J. H. Edwards and F. J. McQuillin, J.C.S. Chem. Comm., 1977, 838.
381 W. Pickenhagen, G. Ohloff, R. K. Russel, and W. D. Roth, Helv. Chim. Acta, 1978,61, 2249.
382 B. B. Snider and T . A. Killinger, J. Org. Chem., 1978, 43, 2161.
Monoterpenoids 37
catalysed hydrogen peroxide epoxidation under buffered conditions (Vol. 8,

p. 12) has been
The well-known photochemical rearrangement of citral has been shown to be
temperature-dependent; at elevated temperatures the major products are the
formyl-migrated (65), with the cis-aldehyde p r e d ~ m i n a t i n g . Sensitized
~~~
photochemical rearrangement of the corresponding geranonitrile at 132 "C yields
predominantly (66),a known acid-catalysed Beckmann fragmentation product of
(65) (66)
a -fenchone ~ x i m e . ~Further ~' details of the Rose Bengal-sensitized photo-
oxygenation of 2,6-dimethylocta-2,6-diene, which was reported earlier (Vol. 4, p.
14), have been published in a kinetic The full paper on the photochemi-
cal irradiation of citral in the presence of methanol and TiCl, (Vol. 6, p. 10) has
been published.256The addition of photochemically generated free radicals to
3,7-dimethylocta-1,6-dieneoccurs selectively at the 6,7-double bond with
bifunctional radical addends and at the 1,2-double bond with monofunctional
radicals, analogous to earlier results (Vol. 7, p. 14) involving manganese(II1)
acetate o x i d a t i o n ~ . ~ ~ '
Treatment of geraniol, nerol, linalool, and their acetates and phosphates with
85o/' phosphoric acid results in essentially similar mixtures of predominantly
cyclic hydrocarbons ( a-terpinene, y -terpinene, isoterpinolene, limonene, p -
cymene, and p-menth-3-ene); the results are rationalized in terms of carbonium
ion structures and stabilities with the interesting observations (i) that limonene
can neither be derived from the a-terpinyl cation nor from (67), into which the
A
(67)
a-terpinyl cation may be converted rapidly by a 1,2-hydride shift, (ii) that the
a -terpinyl cation rearranges in preference to cyclization to bicyclic compounds,
and (iii) that relatively slow deprotonation allows extensive intramolecular
carbonium ion rearrangements to account for significant amounts of iso-
terpinolene and ~-menth-3-ene.~*' A second paper reports rearrangement in
3n3 T. Kametani, H. Nemoto, and K. Fukumoto, Bioorg. Chem., 1978,7,215.
384
F. Barany, S. Wolff, and W. C. Agosta, J. Amer. Chem. SOC.,1978,,100, 1946.
3n5 S.Wolff and W. C. Agosta, J. Org. Chem., 1978, 43, 3627.
386 C. Tanielian and J. Chaineaux, J. Phorochem., 1978, 9, 19.
387 J. H. Edwards, F. J. McQuillin, and M. Wood, J.C.S. Chem. Comm., 1978, 438.
388 J. P.McCormick and D. L. Barton, Tetrahedron, 1978, 34, 325.
aqueous citric acid at pH 2.4; in addition to cyclization (to a-terpineol) and

allylic rearrangement (e.g. to linalool), competitive hydration of the 6,7-double
bond is observed (e.g. to yield 3,7-dimethyloct- l-ene-3,7-diol). The results
suggest that, under the mild conditions used, a-terpineol formation from geraniol
occurs via linalo01.~'~Citral cyclization in aqueous citric acid gives essentially
identical results to those reported earlier (Vol. 8, p. 28).390
The predominant product of polyphosphoric acid cyclization of dehydro-
linalool (cf. Vol. 1, p. 9) is dependent upon the amount of acid and upon the
reaction temperature.391
The regioselective oxidation of 3,7-dimethyloctyl acetate, adsorbed on silica
gel, with gaseous ozone at -78 "C as a function of substrate loading has been
reported in full (without reference to the author's earlier communication; see Vol.
8, p. 29).392Cyclic hydroboration of myrcene with B2H6 followed by cyanidation
(cf. Vol. 7, pp. 17, 18) yields (68) and (69) whereas reaction with thexylborane
results predominantly in cyclic hydroboration [which leads to (68)] with some
expected acyclic h y d r ~ b o r a t i o nFurther
. ~ ~ ~ work with T-ally1 complexes (see also
ref. 229) of myrcene (cf.Vol. 1, pp. 11, 12; Vol. 2, p. 10; Vol. 3, p. 13) includes
alkylation with active methylene compounds (for related pinene alkylation see
Vol. 6 , p. 45); C-1, C-2, (2-3' selectivity depends upon the metal (Pd or Ni), the
phosphine ligand, and the alkylating agent (cf. Vol. 8, p. 29).394The effective
1,2-anti-Markovnikoff addition of sulphinic acids to the terminal double bond of
myrcene has been accomplished using PdC1,-sulphinate salts followed by re-
moval of the palladium from the v-allyl-palladium complex with dimethylgly-
oxime; surprisingly the terminal less-substituted alkene is formed selectively in
contrast to the formation of (70) following prior extrusion of sulphur dioxide.395
(68) (69) (70)

Tsuji has observed that geranyl, neryl, and linalyl acetates undergo elimination to
yield similar ratios of myrcene, cis -ocimene, and trans -0cimene using Pd(OAc)2-
Ph3P.396
The bisulphite adducts of citral have been characterized; interestingly, the 1: 2
citral: bisulphite adduct is (71), analogous to the structure of the piperitone
389 R. L. Baxter, W. A . Laurie, and D. McHale, Tetrahedron, 1978, 34, 2195.
390 D. McHale, W. A . Laurie, and R. L. Baxter, Rivista Ital. Essenze-Profumi, Piante Offic.,Aromi,
Saponi, Cosmet., Aerosol., 1978, 60, 139 (VIIth International Congress of Essential Oils, Kyoto,
October 7-11, 1977, Abstract No. 66).
391 S.p.A. Anic, Belg. P. 852 918 (Chem. Abs., 1978,88, 152 426).
392 A . L. J. Beckwith, C. L. Bodkin, and T. Duong, Austral. J. Chem., 1977, 30,2177.
393 R. Murphy and R. H . Prager, J. Organometallic Chem., 1978,156, 133.
394 R. Baker and R. J. Popplestone, Tetrahedron Letters, 1978, 3575; for related work see ref. 229.
39s Y. Tamaru, M. Kagotani, and Z.-I. Yoshida, J.C.S. Chem. Comm., 1978,367; the formula for (70) is
incorrect in the paper.
396
J. Tsuji, personal communication. Some details of this work have been published; see ref. 244.
Monoterpenoids 39
sodium bisulphite addition compound reported earlier (Vol. 7, p. 34); reaction at

the carbonyl group of (71) yields the 1 : 3 a d d u ~ t . ~ ~ ~
Other papers of interest in this section report addition of arylsulphenyl
chlorides to ci~-2,6-dimethylocta-2,6-diene,~~~ the mild regioselective con-
version of the epoxide (72) into (73) using [Fez(C0)9],398 allylboration of ~ i t r a 1 , ~ ~ ~
(71) (72) (73)

conversion of myrcene into g e r a n y l a ~ e t o n e , cyclophane-monoterpenoid
~~~'~~~
inclusion C O ~ ~ O U ~ dimerization
~S,~'' of 2,6-dimethylocta-1,3,6-trieneusing
nickel complexes,4o1 selective catalytic hydrogenations of ~ i t r a l , ~dehydro-
'~
and gerani01,~'~and syntheses of 7-hydroxycitronellal.40s
linalo01,~'~
Artemisyl, Santolinyl, Lavandulyl, and Chrysanthemyl Derivatives.-Oxidosan-

tolina triene (74) has been isolated from Arternisiu tridentutu together with (75),
the diastereoisomer of a previously reported ester (Vol. 6 , p. 20; see Vol. 7, p. 21
397
G. M. Buchan and G. G. Cameron, J.C.S. Perkin I, 1978,783.
398
K. Hayakawa and H. Schmid, Helv. Chim. Acta, 1977,60,1942.
399
K. Takabe, G. H. Tang, H. Omura, T. Katagiri, and J. Tanaka, Chem. and Ind., 1977,768.
400
Y. Ichikawa, M. Yamamoto, H. Tsuruta, K. Kato, T. Yamaji, E. Yoshisato, and T. Hiramatsu, Ger.
Offen. 2 726 056 (Chem. Abs., 1978,88, 121 459).
401
U. M. Dzhemilev, R. N. Fakhretdinov, and G. A. Tolstikov, Bull. Acad. Sci., U.S.S.R.,Div. Chem.
Sci., 1977, 26,840.
402
D. V. Sokol'skii, A. M. Pak, and M. A. Ginzburg, Doklady Akad. Nauk S.S.S.R., 1978,239,897;
Vestnik Akad. Nauk Kaz. S.S.R., 1978, (4), 48; D. V. Sokol'skii, A. M. Pak, L. D. Rozmanova, and
L. A. Sokolova, J. A p p l . Chem. (U.S.S.R.),1976, 49, 408; D. V. Sokol'skii, A. M. Pak, S. R.
Konuspaev, M. A. Ginzburg, and L. D. Rozmanova, Trudy Inst. Org. Katal. Elektrokhim., Akad.
Nauk Kaz. S.S.R., 1977, 14, 3 (Chem. Abs., 1978, 88, 89857); Y. Ichikawa, T. Yamaji, and
T. Sawaki, Jap. P. 46 008/1977 (Chem. A h . , 1977,87, 136 052); P. S. Gradeff, Fr. P. 2 314 911
(Chem. Abs., 1977,87,136 055); R. S. De Simone and P. S. Gradeff, U.S. P. 4 029 709 (Chem. Abs.,
1977,87, 184 727).
403
D. V. Sokol'skii, A. M. Pak, 0.I. Kartonozhkina, I. N. Bratus, and A. A. Bakhtinov, J. A p p l . Chem.
(U.S.S.R.),1977,50, 1769; D. V. Sokol'skii, A. M. Pak, and 0. I. Kartonozhkina, Zhur. org. Khim.,
1978,14, 953.
404
G. Takagi and S. Teratani, Jap. P. 91811/1977 (Chem. Abs., 1978, 88, 7119); Y. Ninagawa,
Y. Ohmura, F. Nakahara, T. Nakamoto, and T. Kawaguchi, Jap. P. 131 506/1977 (Chern. Abs.,
1978,88, 89 887).
405
Y. Ichikawa and T. Yamaji, Jap. P. 25 70411977 (Chem. Abs., 1977, 87, 136 047), Jap. P.
25 708/1977 (Chem. Abs., 1977,87,136 046); Y. Ogino, Y. Saito, and K. Ito, Jap. P. 48 610/1977
(Chern. Abs., 1977,87, 136 053); E. N. Kiseleva, N. I. Chernousova, T. I. Filatova, K. I. Bogacheva,
B. I. Lavrinenko, Z. I. Agarysheva, R. F. Shilina, and N. A. Smirnova, U.S.S.R. P. 571 472 (Chem.
Abs., 1978, 88, 23 200).
for .a synthesis). Another source of Artemisia tridentata yielded, in addition to

(74), the (3s)-diastereoisomer of (74) which may be converted into artemiseole
(=arthole, Vol. 7, p. 20).406The isolation of (74) and (75) adds biosynthetic
interest to the suggested generation of santolinyl monoterpenoids from chrysan-
themyl alcohol (Vol. 7, p. 185) in that both (1R,3R)- and (1R73S)-chrysanthemo1
are now implicated.
An application of 3,3-dimethylallyl(dipropyl)borane addition to aldehydes233
is the synthesis of the dihydroartemisia alcohol (76; X = H , Y = O H ) . The
corresponding ketone (76; X,Y = 0)has been synthesized by three routes: (i) by
[2,3] sigmatropic rearrangement of the lithio-cyanhydrin ether (77) and in situ
loss of lithium cyanide (cf.Vol. 8, p. 59);407(ii) by Claisen rearrangement of (78),
which is formed by dehydration of the corresponding ally1 N-acylamino-acid
ester, hydrolysis, and oxidative cleavage;4o8and (iii) by the addition of prenyl-
magnesium bromide, with allylic transposition, to methyl dithioisovalerate,
followed by methylation and hydrolysis.365This last method has also been applied
to syntheses of artemisia ketone (79; X,Y = 0) and its non-conjugated isomer,
isoartemisia ketone, starting with the corresponding unsaturated d i t h i o e ~ t e r s , ~ ~ ~ ~
syntheses of which have been competitive double allylic addition
favoured the synthesis of (79; X,Y = 0) via base-catalysed isomerization of
isoartemisia ketone.409a
(77) (79)
The 3H-pyrazoles (80) can be regarded as isoprenoid thiovinylcarbene pre-

cursors; photochemical decomposition of (80) in ethyl prenyl sulphide yields (79;
X = Y = SR), presumably via [2,3] sigmatropic rearrangement of (81), together
with a minor [1,4] sigmatropic rearrangement product; with (80; R = p-tolyl) the
SR
SR I
reaction is almost quantitative and [2,3] sigmatropic rearrangement is favoured

8: 1 over [1,4] sigmatropic rearrangement, resulting in a 65% isolated yield of
406 T. A. Noble and W. W. Epstein, Tetrahedron Letters, 1977,3933; formulae (1) and (3) of this paper
lack a rnethylene group. This paper may be read usefully with that reporting the structure of
artemiseole (227); see ref. 690.
407 B. Cazes and S. Julia, Bull. SOC.chim. France, 1977,925.
408 R . Lohmar and W. Steglich, Angew. Chem., 1978, 9 0 , 4 9 3 .
409 P. Gosselin, S. Masson, and A. Thuillier, Tetrahedron Letters, ( a ) 1978, 2717; ( b ) 1978, 2715.
Monoterpenoids 41
artemisia ketone (79; X,Y = O).410Another synthesis of (79; X,Y = 0)involves

straightforward manipulation of ethyl a~etoacetate.~"
The utility of lithiated senecioamides as monoterpenoid synthons is illustrated
by deconjugative a -prenylation (see Vol. 7, p. 14 for related work) and two-step
reduction to lavandulol (82),235Another synthesis of the lavandulyl carbon
skeleton has been reported earlier.335
v.-
HO
An undergraduate experiment on chrysanthemic acid synthesis has been

p~blished.~ Oxidative
'~ coupling of methyl acetoacetate with 2,5-dimethylhexa-
2,4-diene using manganese(II1)acetate yields-(83),photochemicalrearrangement
of which leads to methyl cis- and trans-chrysanthemates after base treatment.413
Further reports on optimizing syntheses of chrysanthemic acid and some ana-
logues have come from Krief's Isopropylidene-
triphenylphosphorane addition to either diethyl fumarate or diethyl
maleate yields trans-(84; R = Et, X = C02Et) with 100% stereoselectivity;
partial hydrolysis, reduction, and oxidation yields the known and synthetically
useful trans-(84; R = Et, X = CHO) (Vol. 8, pp. 33,34). Entry into the cis series
[viz. cis-(84; R = Et, X = CHO)] was achieved by conversion of the trans-diester
(84; R = Et, X = C02Et)into the cis-monoester (84; R = Me, X = C02H)via the
corresponding cis -anhydride.414The successful addition of phosphoranes to

methyl trans-4-oxobutenoate (Vol. 8, p. 33) has now been shown to proceed via
initial addition to the carbonyl group to yield a betaine which is essential to
cyclopropane formation by further addition to the conjugate double bond; access
to chrysanthemicester analogues is thus easy in a two-step one-pot A
useful and industrially less dangerous alternative to the synthesis of chrysan-
themic acid by diazoacetate addition to 2,5-dimethylhexa-2,4-dieneconsists of
malonate addition to the corresponding monoepoxide to yield, after hydrolysis,
410 M. Franck-Neumann and J. J . Lohmann, Tetrahedron Letters, 1978,3729.
411 0 .P. Vig, A. S. Sethi, M. L. Sharma, and S. D. Sharma, Indian J. Chem., 1977,15B, 951.
412 P. F. Schatz, J. Chem. Educ., 1978, 55,468.
413 K. Ohkata, T. Isako, and T. Hanafusa, Chem. and Ind., 1978, 274.
414 M. J. Devos, J. N. Denis, and A. Krief, Tetrahedron Letters, 1978, 1847.
'15 M. J. Devos and A. Krief, 2nd I.U.P.A.C. International Symposium on Organic Synthesis, Jerus-
alem-Haifa, Israel, September 1978, Abstracts, p. 25; A. Krief, personal communication.
pyrocine (85),416another synthesis of which is a minor modification of an earlier

synthesis (Vol. 8, p. 34), viz. Michael addition of 2-methylprop-1-enylmagnesium
bromide to the butenolide (86).417SnC1,-catalysed allyloxymethyl chloride addi-
tion to methyl 4-methylpent-3-enoate, followed by ether cleavage and base-
catalysed cyclization, yields the cis -chrysanthemate precursor (87);alternatively,
addition of 2-bromoethyloxymethy1 chloride and base cyclization yields truns-
(84; R = Me, X = CH20CH2CH2Br)which on treatment with Zn-MeOH yields
trans-(84; R = Me, X = CH20H).418
Further papers of interest in this section concern the decomposition of alkyl
diazoacetates in 2,5-dimethylhexa-2,4-dienein the presence of chiral copper
complexes (cf.Vol. 8, p. 33),419a revision of the 2-pyrazoline structures [viz. to
(SS)] described in an early chrysanthemumdicarboxylic acid and
(85) (86) (87) (88)

syntheses of me thy1 arylmet h yl 2,2 -dimethyl-3 - (2'-methylprop-1'-en y1)cyclo-
~ ~ ~the C9 compound salvan (2-isopropylhexa- 1,4E-
p r o p y l p h o s p h o n a t e ~and
diene).422
6 Naturally Occurring Halogenated Monoterpenoids

Last year's Report (Vol. 8, p. 31) erroneously implies that the X-ray structure of
costatolide has been determined.
The past year has seen further advances in the isolation and characterization of
new compounds, with most progress being in the area of cyclic halogenated
monoterpenoids. The only new acyclic example is (89) from Aplysia l i r n a c i n ~ . ~ ~ ~
416
TC1
Br ,CH '
M. J. Devos and A. Krief, Tetrahedron Letters, 1978, 1845. For similar work, see P. D. Klemmensen
and H. Kolind-Andersen, Ger. Offen. 2 732 456 [Chem. A h . , 1978, 88, 136 190; formula (111)of
this abstract lacks gem-dialkyl suhstituents].
417
S. Torii, H. Tanaka, and Y. Nagai, Bull. Chem. SOC.Japan, 1977,50, 2825.
418
C. F. Garbers, M. S. Beukes, C. Ehlers, and M. J. McKenzie, Tetrahedron Letters, 1978, 77.
419
( a )T. Nagase, S. Nakamura, T. Aratani, and Y. Yoneyoshi, Jap. P. 25 755/1977 (Chem. A h . , 1977,
87, 136 048); (6) T. Aratani, Shokubai, 1977, 19, 327.
420
H.-D. Scharf and J. Mattay, Chem. Ber., 1978, 111, 2206.
421
J. J. Reid and R. S. Marmor, J. Org. Chem., 1978,43,999.
422
S. D. Sharma and R. C. Aggarwal, Indian J. Chem., 1977,15B, 950.
423
F. Imperato, L. Minale, and R. Riccio, Experientia, 1977, 33, 1273.
Monoterpenoids 43
Faulkner has now published full details of five new compounds reported last year
from Plocamium cartilagineum ;the only modification is that one of them [Vol. 8,
p. 31, formula (SS)] is now reported as (90)424in keeping with the reassigned
structure of violacene (2).25An interesting, but not fully characterized, new minor
component (91; X,X,X, = C1, C1, Br) adds novelty with an axial C-5 methyl
(90) (91)
group.424A second report of new compounds from P. cartilagineum confirms2'
the absolute configuration (1; X = Br) of a compound isolated previously by
Faulkner [Vol. 8, p. 31, formula (89)l"""and reports one of only two known
naturally occurring examples of a dimethylethylcyclohexane monoterpenoid with
a bromovinyl side-chain (4).27The other is ochtodene (92; X = C1, Y = Br) which
has been isolated from Ochtodes secundiramea together with ochtodiol (93) and
chondrocole A (94),425awhose structure has now been reassigned (cf. Vol. 6, p.
47) as a result of the X-ray structure determination of chondrocolactone (3)from
Chondrococcus hornemanni.26 The significance of a second report of new
compounds from Ochtodes species cannot be assessed properly at present; 0.
secundirumea is reported to yield (92; X = Br, Y = C1) and 0. crockeri to yield
(95).4256Crews has published structural details of a number of compounds
(92) (93) (94) (95)
isolated from Plocamium cartilagineum and P. violaceum (cf.Vol. 8, p. 31). The

absolute stereochemistry of plocamene B is now established as (96) [and not as
Vol. 6, p. 33, formula (1 5 l)];plocamene C is identical with violacene 2 (1 ;X = C1)
[and not as Vol. 7, p. 20, formula (74) or Vol. 8, p. 31, formula (86)]; in view of the
X-ray structure of violacene (2),25plocamene D must be the mirror image of that
reported previously [Vol. 8, p. 31, formula (87)], viz. (97; X=Cl). Two new
compounds are plocamene D' (97; X = Br) and plocamene E (98) which may be
obtained from plocamene C (1; X = C1) by HBr elimination and isomerized into
plocamene B (96).426Further new compounds are reported to be (99) from
Australian P. curtilagil~eurn~~~ and mertensene (100)from P. mertensii, although
Crews has expressed over the stereochemical assignment of the two
424 M. D. Higgs, D. J. Vanderah, and D. J. Faulkner, Tetrahedron, 1977, 33, 2775.
425 0. J. McConnell and W. Fenical, ( a ) J. Org. Chem., 1978, 43, 4238; (b) 175th A.C.S. Meeting,
Annaheim, California, March 1978, Abstracts AGFD, No. 26. It is possible that (92; X = Br, Y = C1)
is a misprint of (92; X = C1, Y = Br).
426 P. Crews, E. Kho-Wiseman, and P. Montana, J. Org. Chem., 1978, 43, 116.
gem-substituted centres in (100) which is especially interesting in view of the

similarity between the spectroscopic data presented for and the limited
c1
(99)
spectroscopic data presented for (91 ; X,X,X = C1, C1, Br);424 a third new
compound (1; X = Br)427has already been reported (Vol. 8, p. 31).424,27A
component (101) from Desmia (Chondrococcus) hornemanni which was omitted
from earlier has now been synthesized together with (102) and
perillyl bromide (103; R = CH,Br) by brominative cyclization of myrcene using
2,4,4,6-tetrabromocyclohexa-2,5 -dien- 1-one.428b
Further work (cf. Vol. 8, p. 30) has indicated the considerable geographic
variation in the halogenated monoterpenoid content of P, c a r t i l u g i n e ~ m . ~ ~ ~ * ~ ~
Both plocamene B (96)and violacene (2) exhibit growth inhibition against
mosquito and antibacterial activity against Staphylococcus aureus has
been reported for ochtodene (92; X = C1, Y = Br).425u
N.m.r. spectroscopy has been used extensively in the structural elucidation of
halogenated monoterpenoids (e.g. refs. 424,426,427); two further papers which
report useful data concern 13Cn.m.r. y-effects115and the differentiation of some
brominated carbons from chlorinated carbons due to shortened 13C n.rn.r.
spin-relaxation times and reduced values of nuclear Overhauser e n h a n ~ e m e n t . ~ ~ ’
427 R. S . Norton, R. G . Warren, and R. J . Wells, Tetrahedron Letters, 1977, 3905.
428 (a) N. Ichikawa, Y. Naya, and S . Enomoto, 18th Symposium of Terpenes, Essential Oils, and
Aromatic Chemistry, 1974, Abstracts, p. 67; (6) K. Yoshihara and Y. Hirose, Bull. Chem. SOC.
Japan, 1978, 51, 6 5 3 . The formula for myrcene is misprinted in the latter.
429 J. S . Mynderse and D. J. Faulkner, Phytochemistry, 1978, 17, 237.
43n R. S . Norton, Tetrahedron, 1977, 33, 2577.
Monoterpenoids 45
7 Monocyclic Monoterpeaoids
Cyc1obutane.-A tricyclic acetal named lineatin has been isolated from the frass
of the Douglas fir beetle Trypodendron lineatum ; structural elucidation and
synthesis have not distinguished between (104) and (105).431
Mori has synthesized the natural (lR,2S)-(+)-grandisol (106) and its enan-
tiomer in an improved synthesis reminiscent of that reported by Cargill and
Wright (Vol. 6, p. 21) and based upon photochemical cycloaddition of ethylene to
3-ethoxycarbonylcyclopent-2-enone;optical purity measurements on the
intermediate alcohols [e.g. (107)], using the n.m.r. shift reagent [Eu(facam)J,
established an 80% optical purity for synthetic (106) with an optical rotation in
agreement with that reported by Magnus (Vol. 7, p. 22).432The full paper on the
Wenkert synthesis of racemic-(106) (Vol. 7, p. 22) has been
Fragranol and grandisol derivatives [e.g. (108; 43%)] have been formed pre-
dominantly (72%) by treating 6,7-epoxygeranyl t-butyl sulphide with BuLi-1,2-
bis(dimethylamino)ethane,although the t-butylthio-group in (108) has prevented
elaboration into f r a g r a n 0 1 . ~ ~ ~
SBu'
Cyclopentanes, 1ridoids.-The taxonomic significance of iridoids in Tubiflorue

and the occurrence of secoiridoids in the G e n t i a n a ~ e a ehave
~ ~ ~been
reviewed. Some papers of related synthetic interest have been discussed
earlier -254.380-385
The dial (3R,8S)- (109), named dehydroiridodial, has been isolated from
Actinidia polygama and synthesized from (-)-limonene via (4S,8S) -p- menth- 1-
en-9-01 of knowns1 absolute c ~ n f i g u r a t i o nthe
; ~ ~diastereoisomeric
~ chrysomeli-
dial [(3S,8S)-(109)] (Vol. 8, p. 35) has been synthesized similarly from
431 J. G. MacConnell, J. H. Borden, R. M. Silverstein, and E. Stokkink, J. Chern. Ecol., 1977, 3, 549.
432 K. Mori, Tetrahedron, 1978, 34, 915.
433 E. Wenkert, D. A. Berges, and N. F. Golob, J. Arner. Chern. SOC.,1978,100, 1263.
434 V. Rautenstrauch, J.C.S. Chern. Cornm., 1978, 519.
435 R. Hegnauer and P. Kooiman, Plantu Med., 1978, 33, 1.
436 W. G. van der Sluis and R. P. Labadie, Pharrn. Weekblad, 1978,113,21.
437 K. Yoshihara, T. Sakai, and T. Sakan, Chern. Letters, 1978, 433.
e ~ ~is~ now reported by Blum et al. as a single component from

( + ) - l i m ~ n e n and
Gastrophysa ~ y a n e a . ~ ~ ~
From related synthetic work in which epiplagiolactone was synthesized from
(4K,8R)-p-menth- 1-en-9-01, the ( S , S )- absolute configuration reported pre-
viously [Vol. 8, p. 35, formula (120)] for the C-4 epimeric plagiolactone from
Plagiodera versicoloru confirms the close relationship to the co-occurring chry-
somelidial [ ( 3 S , 8 S ) - (109)]438from which it was a minor product of autoxidata-
t i ~ nInterestingly
. ~ ~ ~ no lactones were observed corresponding to those sugges-
ted439as minor products from Gastrophysa cyanea, uiz. (110) and the known
(111) (Vol. 3, p. 26; Vol. 8, p. 35, ref. 324). Another oxygenated cyclopentane
(112) from Turkish tobacco (cf. Vol. 6 , p. 27) is probably a nor-is~prenoid.~~'
(109) (110) (111) (112)

Another report of the isolation441of the dolichodials and dolicholactone from
Teucriurn rnarurn and their has appeared. The structure of nitro-
polyzonamine (10) has been revised (Vol. 6 , p. 13).38
Related synthetic work concerns the preparation of 2-isopropyl-5-methyl-
c y ~ l o p e n t a n o n esyntheses
,~~~ of a number of chiral cyclopentanoid aldehydes and
ketones and (113) (cf. Vol. 8, p, 38),443and a number of unsuccessful attempts to
synthesize genipic
9 (113)
Popov has summarized the J1.9 coupling constants for a number of iridoids and
examined the relationship of their values to the position and stereochemistry of
substituents in the cyclopentane ring.445The correlation of absolute configuration
438
J. Meinwald and T. H. Jones, J. Amer. Chem. SOC.,1978,100, 1883.
439
M. S. Blum, J. B. Wallace, R. M. Duffield, J. M. Brand, H. M. Fales, and E. A. Sokoloski, J. Chem.
Ecol., 1978, 4 , 4 7 .
440
T. Chuman, H. Kaneko, and M. Noguchi, Agric. and Biol. Chem. (Japan), 1978,42, 203.
44 1
( a ) C. Beaupin, J.-C. Rossi, J. Passet, R. Granger, and L. Peyron, Rivista Ztal. Essenze-Profumi,
Piante Ofic., Aromi, Saponi, Cosmet., Aerosol., 1978, 60, 93; ( 6 ) C. Beaupin, R. Granger, J.-C.
Rossi, J. Passet, and L. Peyron, ibid., 1977,59,369;the Chemical Abstract (Chem. Abs., 1978,88,
11 723) incorrectly reports this as the first isolation of these compounds from the plant kingdom. See
Vol. 7, p. 23.
442
B. S. Kulkarni and A. S. Rao, Org. Prep. Proced. Internat., 1978, 10,73.
443
G . L. Lange, E. E. Neidert, W. J. Orrom, and D. J. Wallace, Canad. J. Chem., 1978,56, 1628. For
related work, see M. Pesaro and J.-P. Bachmann, J.C.S. Chem. Comm., 1978,203; J. Kulesza and
M. Sikora, Rivista Ital. Essenze-Profumi, Piante Ofic., Aromi, Saponi, Cosmet.,Aerosol., 1978,60,
141 (VIIth International Congress of Essential Oils, Kyoto, October 7-1 1,1977, Abstract No. 74).
444
J. K. Whitesell and R. S. Matthews, J. Org. Chem., 1978, 43, 1650.
445
S. S. Popov, Izuest. Khim. (Bulgaria),1976,9,459;the paper suggests that the structure of unedoside
may be incorrect without reference to Rimpler's reassignment (Vol. 7, p. 24).
Monoterpenoids 47
of the valepotriates and c.d. data has been H.p.1.c. data on the
v a l e p o t r i a t e ~and
~ ~ ~on iridoids from Gentiana species448have been reported.
The isolation of ulmoside (114) from Eucommia ulmoides is of interest because
of its p-isomaltose residue.449
A-@
H
HOCH 0-p-isomaltose
The isolation of three naturally occurring fulvoiridoids (Vol. 8, p. 38), uiz.

cerbinal(l15; R' = C02Me, R2= CHO), cerberic acid (115; R' = C02Me, R2 =
C02H),and cerberinic acid (115;R' = C02H,R2= CHO), from Cerbera manghas
may reflect mild hydrolysis in viuo of co-occurring C16irid~ids.~"Other new Clo
iridoid derivatives are pulchellosides 1451aand 114516 [(116) and its C-8 epimer
respectively] from Verbena pulchella, the xylose-containing montinioside (117)
from Montinia c a r y o p h y l l a ~ e aand
, ~ ~four
~ isomeric pairs of novel allose-contain-
ing iridoid glycoside esters - named opulus iridoids I-IV [ 118; R1= H or
Ac; R2= Ac (C-2', C-3' only), H (C-4' and/or C-6'), P-D-xylopyranosyl
(C-4')] - frdm Viburnum 0 p u 1 u s . ~New ~ ~ valepotriates include acetoxyhy-
droxydidrovaltrate (119; R = Ac) and the previously unreported
isovaleroxyhydroxydidrovaltrate (119; R = COCH2CHMe2)from Centranthus
R'
R2 m0 --
OGlu
HO'
R'OCH, 0 or
446 A . Konowal, G . Snatzke, and P. W. Thies, Tetrahedron, 1978,34, 253.

447 G. Tittel and H. Wagner, J. Chromatog., 1978,148,459.
448 0.Sticher and B. Meier, Pharm. Acta Helv., 1978, 53,40.
449 A . Bianco, C. Bonini, M. Guiso, C. Iavarone, and C. Trogolo, Gazzetta, 1978,108, 17.
4s0 F. Abe, H. Okabe, and T. Yamauchi, Chem. and Pharm. Bull. (Japan), 1977,25, 3422.
451 S. Milz and H. Rimpler, Tetrahedron Letters, ( a ) 1978, 895; ( b ) 1978, 3549.
452 R. Dahlgren, S. R. Jensen, and B. J. Nielsen, Botan. Notiser, 1977, 130, 329.
453 K. Bock, S. R. Jensen, B. J. Nielsen, and V. Norn, Phytochemistry, 1978, 17, 753.
ruber where they co-occur with the known (Vol. 7, p. 25) valtrate, didrovaltrate,
~ ~ ~ structures, together with (119; R = COBu'), are depic-
and a c e ~ a l t r a t ewhose
ted incorrectly in a second paper and in the corresponding Chemical
1 0-Deacetylasperulosidic acid and asperulosidic acid have been isolated as
natural products from Rubia tinctorum and R . ~ e r e g r i n a ~(for
~ ~their
" isolation as
artefacts see ref. 456b), and monotropein methyl ester (8; R = Me) from Galium
mo/l~go.~~~"
Tietze et al. have described efforts to convert 7 - 0 - acetyl-loganin aglycone into
loganin and the corresponding a- glucoside by standard glucosylation proce-
d u r e ~ . ~ ~ ~
Acid-catalysed rearrangement of (120), a synthetic reduction product of
lamiide, to (121) has been
CHO
The secoiridoid (*)-gentiolactone (9) has been isolated from Gentiana

~ ~the full paper on naucledal (Vol. 7, p. 26) includes data on its C-4
p ~ r p u r e aand
epimer (according to the iridoid numbering system used in these Reports; the
authors have named this compound 3-epinaucledal) which accompanies naucle-
dal on rearranging sweroside aglucone (122; R = H) in aqueous ~ y r i d i n e . ~ ' ~
(*)-Sweroside aglucone 0-methyl ether (122; R = Me) and secologanin 0-
methyl ether (123; R = Me) have been synthesized efficiently by Partridge et al. as
an extension of their earlier work (Vol. 4, pp. 25,26) based upon the photoadduct
of methyl diformylacetate and cyclohexa-1,4-diene (Scheme 2).460Secologanin
(123; R = p-Glu) has been converted into the useful Cinchona alkaloid synthons
dihydrorneroq~inene~~'" and r n e r ~ q u i n e n e ~via
~ ~ 'sodium cyanoborohydride
reductive amination. In further bicyclo[3,3,0]octane synthetic work directed
towards iridoids, the essential features of which have been reported previously
(Vol. 8, p. 36; for related work, see also Vol. 8, pp. 37,38), Whitesell et al. have
synthesized sarracenin (124), via Baeyer-Villiger oxidation of (125) followed by
4s4 N. Handjieva, S. Popov, and N. Marekov, Phytochemistry, 1978,17,561. For earlier reportsof (119;
R = C O C H ~ C H M ~ Zsee ) , J. L. Laufer, B. Seckel, and J. Zwving, Pharm. Weekblad, 1970,105,609,
and T. Adret, I. Iglesias, R. San Martin, and M. Torrent, Planta Med., 1975,27, 194.
45s B. Eierrnann and P. T. A. Seym, Deut. Apoth.-Z., 1977,117,1204 (Chem.Abs., 1977,87,157 067).
4s6 ( a ) A . Bianco, M. Guiso, C. Iavarone, P. Passacantilli, and C. Trogolo, Gazzetta, 1978, 108, 13;
(6) H. Inouye, M. Okigawa, and N. Shirnokawa, Chem. and Pharm. Bull. (Japan), 1969,17,1949.
457 ( a ) L.-F. Tietze, U . Niemeyer, and P. Marx, Tetrahedron Letters, 1977, 3441; (6) L.-F. Tietze and
U. Niemeyer, Chem. Ber., 1978, 111, 2423; ( c ) L.-F. Tietze and P. Marx, ibid., 1978, 111, 2441
[formula (10) of this paper lacks a C-7 acetyl group].
458 A. Bianco, C. C. Bonini, M. Guiso, C. Iavarone, and C. Trogolo, Tetrahedron Letters, 1978,4829.
4sq J. Purdy and S. McLean, Canad. J. Chem., 1977,55,4233.
46" C. R. Hutchinson, K. C. Mattes, M. Nakane, J. J. Partridge, and M. R. Uskokovic, Helv. Chim. Acta,
1978,61, 1221.
461 R. T. Brown and J. Leonard, ( a ) Tetrahedron Letters, 1978, 1605; ( b )J.C.S. Chem. Comm., 1978,
725.
Monoterpenoids 49
ae. OH
4
~e OMe
HO
OMe
i v i , vii
O H C G M e
OR
-viii-x
I;:g OR
(123) (122)
Reagents: i, MeOH-H+; ii, OsO,; iii, HIO4, pH 5; iv, NaBH4-PriOH-H20, 0 OC; v, separation;
vi, o-nitrophenylselenocyanate-PPh3-py; vii, H202; viii, OH--H,O-Pr'OH; ix, CH2N2;
X,DCC-DMSO-PY-CF~CO~H
Scheme 2
o&2Me: H
O*0
I OH
H
(124) (125) (125a)
reduction and reductive ozonolysis, in a scheme readily adaptable to the synthesis

of chiral and radiochemically labelled
The C9 monoterpenoid alkaloid jasminidine (126) has been isolated from
Syringa v ~ l g a r i s(+)-Acthidine
.~~~ (127) is obtained by hydroxylamine treatment
(126) (127)
462
(a) J. K. Whitesell, R. S. Matthews, and A. M. Helbling, J. Org. Chem., 1978, 43, 784; (b) J. K.
Whitesell, R. S. Matthews, P. K. S. Wang, and A. M. Helbling, 175th A.C.S. Meeting, Annaheim,
California, March 1978, Abstracts ORGN, No. 176. Details of an enantio-divergent route to the
related xylornollin (125a)in the latter cannot be assessed at this time; formula (4)of this abstract is in
error and the formula given for (-)-xylomollin [uiz.(125a)lrepresents a structural revision ( c f .Vol.
8, p. 39) subsequently confirmed by Hutchinson et ul.34a
463
H. Ripperger, Phytochemistry, 1978,17, 1069.
of (128), the product of treating the acid chloride (129) with base, presumably via
[ 1,5] sigmatropic hydrogen migration in the intermediate keten.464
(128) (129)
p-Menthanes.-Reviews of CY - ~ h e l l a n d r e n e , ~/3 ~- ~
’ h e l l a n d r e n eand
, ~ ~carvone
~
(18) have been published.
The trio1 (130) has been isolated from the micro-organism Fusicoccum amy -
g d ~ l ithe
, ~acid
~ ~(131)from Cedrus deodara is probably a n o r - s e ~ q u i t e r p e n o i d , ~ ~ ~
the thymoquinol ether (132) is reported to occur in Blumea m e m b r a r ~ c e aand ,~~~
Bohlmann et al. have isolated many new thymol derivatives from a number of
different species.471Doubts over the presence of a y-terpinene monoepoxide
reported earlier (Vol. 5, p. 22) in Origanum heraczeoticum, and of its synthesis
from y-terpinene by peracid epoxidation, have been ~ o n f i r m e d . ~ ’ ~
Further 13C n.m.r. data have been published on isomeric menthyl (cf.Vol. 7,
pp. 5, 29) and carvomenthyl alcohols and some derivatives.473‘H N.m.r. data
include [Eu(dpm),] methyl shift assignments in the menthols, the menthones, two
carvomenthols, the isopulegols, the carveols, carvone, carvotanacetol, and
carvotanacetone, together with the relevant and an analysis of
464 J. D. Wuest, A. M. Madonik, and D. C. Gordon, J. Org. Chem., 1977,42,2111; this synthesis was
inadvertently omitted from last year’s Report.
4h5 B. Singaram and J. Verghese, Perfumer and Flavorist, 1978,2(7), 33.
466 J. Verghese, Indian Perfumer, 1976, 18, 47 (Chem. Abs., 1977, 87, 201 776 incorrectly refers to
1975).
467 B. Singaram and J. Verghese, Perfumer and Flavorist, 1977,2(3),47.
468 C. G. Casinovi, G. Grandolini, L. Radics, and C. Rossi, Experientia, 1978, 34, 298.
46q S. Krishnappa and S. Dev, Tetrahedron, 1978, 34, 594.
470 K. P. Bokadia, S. K. Joshi, andM. M. Bokadia, Acta Cienc. Indica, 1976,2,239 (Chem. Abs., 1977,
87, 141 107).
471 ( a ) F. Bohlmann and N. L. Van, Phytochernistry, 1977,16, 1765; (6)F. Bohlmann and C. Zdero,
ibid., pp. 1773, 1854, ( c )F. Bohlmann, P. K. Mahanta, A. Suwita, A. Suwita, A. A. Natu, C. Zdero,
W. Dorner, D. Ehlers, and M. Grenz, ibid., p. 1973; ( d )F. Bohlmann, P. K. Mahanta, J. Jakupovic,
R. C. Rastogi, and A. A. Natu, ibid., 1978, 17, 1165.
472 W. Rojahn and E. Klein, Dragoco Report (Ger. Edn.), 1977, 24, 172.
473 J. Firl, G. Kresze, T. Bosch, and V. Arndt, Annalen, 1978, 87.
474 T. Iida, S. Ibaraki, and M. Kikuchi, Agric. and Biol. Chem. (Japan), 1977,41,2471; see also Vol. 5,
p. 3.
Monoterpenoids 51
p-menth-4-en-3-one and its carbonyl derivatives.475Using deuterium-labelled

compounds, an unusual 1,2-elimination of water has been shown to be preceded
by ring cleavage to the extent of 30% in the molecular ion of the (+)-dihy-
drocarveol (133; X = OH) but not apparently in that of its C-2 epimer or the
corresponding c a r v o m e n t h o l ~ in
;~~the
~ absence of physical data on the dihy-
drocarveols and the corresponding [ 1, 3 , 3 - 2 H 3 ] - ~ ~ m p ~however,
~ n d ~ , these
results must be interpreted with caution since (+)-dihydrocarveol is depicted as
(-)-neodihydrocarveo1(133; X = OH, C-2 epimer) and (133; X = OH) is named
(133)
(-)-dihydrocarveol. Other m.s. data concern p-menth-4-en-3-one and its
carbonyl derivatives,475 and the monoterpenoid-related di-o -thymotide and
t r i - o - t h y m ~ t i d e The
. ~ ~ ~absorption and c.d. spectra of a- and P-phellandrene in
solution (to 160 nm) and in the gas phase (to 135 nm) have been a n a l y ~ e dThe .~~~
i.r. 0 - H stretching frequencies of isopulegol and neoisopulegol have been
assigned to specific hydrogen-bonded ~ o n f o r m a t i o n s Some . ~ ~ ~ thermophysical
data for (-)-menthol vapour have been Fortunately the absolute
configuration of (+)-carvone [(4S)-(18)] is in agreement with that derived by
indirect chemical correlation ( ! ) . 5 5 Analytical data include a colorimetric method
for determining thym01,~~l quantitative determination of (*)-trans-sobrerol by
g . l . ~ . and ~ g.1.c. determination of limonene and 1,8-cineole in oils of
, ~ ~the
peppermint .483
The conversion of (3R)-(+)-citronella1 in to (-)-isopulegol is well known (Vol.
4, p. 28), although this and related (Vol. 7, p. 30) work is not cited in an
examination of Lewis acid catalysis in which ZnBrz gives optimum results [70%
yield, 94% (-).-isop~legol].~~~ Another 1,2-carbonyl transposition procedure
(Scheme 3) converts menthone via the tosylhydrazone (134) into carvomenthone
(135) although in lower yield ( 4 8 ' / 0 ) ~ ~than ~ the epoxysilane route reported
475 B. Singaram, G. N. Saraswathi, and J. Verghese, Indian J. Chem., 1977, 15B, 526; the name
p-menth-3-en-5-one is used in this paper.
476 R. Robbiani, H. Biihrer, H. Mandli, D. KovaEeviC, A. Fraefel, and J. Seibl, Org. Mass Spectrometry,
1978,13,275; carvone (18) is incorrectly identified in this paper also.
477 G. M. Farias and B. D. Hosangadi, Indian J. Chem., 1977,15B, 997.
478 K. P. Gross and 0. Schnepp, J. Chem. Phys., 1978,68, 2647; for related work, see Vol. 8, p. 5 .
479 L. Ananthasubramanian and S. C. Bhattacharyya, J.C.S. Perkin ZZ, 1977, 1821.
480 C. Becker, H. Reiss, and R. H. Heist, J. Chem. Phys., 1978,68, 3585.
481
M. A. Korany, N. Abdel-Salam, and M. Abdel-Salam, J. Assoc. Ofic. Analyt. Chemists, 1978, 61,
169.
482 J. L. Fibregas, Analyst, 1977, 102, 777.
483 A. M. Humphrey, K. Goodhead, J. H. Greaves, W. S. Matthews, D. A. Moyler, R. G. Perry,
J. Ridlington, R. A. Stocks, and,G. Watson, Analyst, 1978, 103, 375.
484 Y.Nakatani and K. Kawashima, Synthesis, 1978, 147.
485 T. Nakai and T. Mimura, 2nd I.U.P.A.C. International Symposium on Organic Synthesis, Jerusalem-
Haifa, Israel, September, 1978, Abstracts, p. 6; T. Nakai, personal communication. For related
eliminations, see ref. 54a; Vol. 7, p. 34; Vol. 8, p. 45.
Reagents: i, Bu"Li (2 equiv.), THF-TMEDA (2 : l ) , -50 to -30 "C; ii, MeSSMe (1 equiv.); iii,
Bu"Li (1 equiv,); iv, room temperature, 5-20 h; v, H20; vi, HgCl2 (2-3 equiv.),
MeCN-HzO (3 : l ) , reflux, 5 h
Scheme 3
earlier;'" intermediate carbanions such as (136) promise to be synthetically

useful. A fourth paper directed towards the synthesis of (+)-8-phenylmenthyl
acrylate, which is an efficient chiral director in Diels-Alder cycloaddition reactions
(Vol. 7, p. 4), follows CuI-catalysed conjugate addition of phenylmagnesium
bromide to the readily accessible (R)-( + )-pulegone [ ( l R ) - (21)] by experimental
improvements on a previously reported 1,3-carbonyl-transpositionscheme (Vol.
5, p. 25).486Limonene has been converted into (137) via lead tetra-acetate
oxidation to (+)-8-hydroxy-p-menth-l-en-9-y1 acetate and the corresponding
(+)-uroterpenol followed by treatment with P ~ ( O A C ) ~Hydrolysis .~'~ of the
1,2-adduct of the lithio-derivative of methyl methylthiomethyl sulphoxide to
4-isopropylcyclohex-2-enone yields the non-naturally occurring (1 38).488
CHO
I I
(137) (138)
Syntheses of the [ 1,3,3-2H3]dihydrocarvones,[ 1,3,3-2H3]neodihydrocarveol,
[ 1,3,3-2H,]dihydrocarveol, [ 1,3,3-2H3]carvomenthol, and [ 1,3,3-2H3]ne~car-
vomenthol have been Further syntheses of interest concern
[l-2Hl]neocarvomenthol, [2-2H,]-(1R,2R,4R)-p-menthan-l-ol, [2-*H1]-
(lS,2S,4R)-p-menthan-l-01, [2-2Hl]-(2R,4R)-p-menth-1(7)-ene, and [2-*H,]-
(2S,4R)-p-menth-l (7)-ene;489 the c a r v e y l a r n i n e ~ ; ~ stereospecific
~~ trans-
formations of (+)-dihydrocarveyl tosylate (133; X = OTs) and (+)-neodihy-
drocarveyl tosylate into (lS,2R,4S)-, (1S,2S,4S)-, and (lR,2R,4R)-2-amino-
trans-p- menthan-8-01 via a z i d o l y ~ i s ; and
~ ~ ' an extension of previously reported
486
H. E. Ensley, C. A. Parnell, and E. J. Corey, J. Org. Chem., 1978,43,1610; for related work, see Vol.
7, p. 30 and Vol. 8, p. 40.
487
M. Nomura, Y. Fujihara, and Y. Matsubara, Nippon Kagaku Kaishi, 1978, 1182.
488 K. Ogura, M. Yamashita, and G.-I. Tsuchihashi, Tetrahedron Letters, 1978, 1303.
489
P. Sundararaman and C. Djerassi, TetrahedronLetters, 1978, 2457.
49n S . W. Markowicz and B. Bochwic, Polish J. Chem., 1978,52,671.
491 2.Chabudzinski, Z. Rykowski, and H. Orszanska, Polish J, Chem., 1978,52,767; formulae (13) and
(16) of this paper lack azide groups.
Monoterpenoids 53
(Vol. 8, p. 40) work to synthesize the benzofuranone (139) and related

compounds by acid ion-exchange resin rearrangement of the corresponding
a l d e h ~ d o a c e t a t eLast
. ~ ~ ~year’s Report omitted mention of the routine synthesis
of ( 8 R ) - ( + ) -and (8S)-(+)-[9-2Hl]-a-terpineol via epoxide reduction (Vol. 8, p.
42, ref: 371) and syntheses of some deuteriated pulegones and pulegone tosyl-
hydra~ones.~~~
(139)
Limonene is metabolized predominantly to (+)-perillic acid (103; R = C02H)
by Pseudomonas incognita, presilmably via C-7 h y d r o ~ y l a t i o nwhich
, ~ ~ ~ has also
been reported in the conversion of a -terpineol into 7-hydroxy-cu -terpineol in
further work (see Vol. 8, p. 26) on callus cultures of Nicotiana t a b a ~ u r nand~ ~is~
also presumed to be involved to account for the isolation of oleuropeic acid (140)
CO, H
I
A OH
(140)
in further (see Vol. 7, p. 9) a -terpineol metabolic studies using P. a e r u g i n o ~ aA. ~ ~ ~

more thorough investigation of the microbial conversion of (-)-menthone by a
Pseudomonas putida strain indicates that the new metabolite (3R,6S)-trans-(19)
may be the precursor of the ring-opened metabolites reported earlier (Vol. 8, p.
42).495Noma has reported further work on the copversion of carvone (18) by P.
ovalis (cf. Vol. 5 , p. 24; Vol. 6, p. 12),496and Candida cylindrusae has been used
to resolve (*)-menthol via preferred valerate ester formation from the laevoro-
tatory isomer.497
Double-bond isomerism by reversible ene reaction using sulphur dioxide may
be interrupted in the presence of D20, which decomposes the intermediate allylic
492 K. J. Divakar, B. D. Kulkarni, and A. S. Rao, Indian J. Chem., 1977, 15B,849.
493 T. Suga and T. Hirata, Rivista Ital. Essenze-Profumi, Piante Offic.,Aromi, Suponi, Cosmet., Aerosol.,
1978, 60, 136 (VIIth International Congress of Essential Oils, Kyoto, October 7-11, 1977,
Abstract No. 50).
494 K. Tadasa, Agric. and Biol. Chem. (Japan), 1977,41, 2095.
495 0. Nakajima, R. Iriye, and T. Hayashi, Nippon Nogei Kuguku Kaishi, 1978, 52, 167.
496 Y. Noma, Nippon Nogei Kagaku Kuishi, 1977, 51, 463; Y. Noma and C. Tatsumi, Riuistu Itul.
Essenze-Profumi, Piante Ofic., Aromi, Suponi, Cosmet., Aerosol., 1978,60,136 (VIIth International
Congress of Essential Oils, Kyoto, October 7-11, 1977, Abstract No. 51).
497 M. Nakayama, Y. Yamaguchi, H. Machida, S. Iwasaki, A. Komatsu, and A. Shinoda, Jap. P.
51 09511977 (Chem. Abs., 1977,87, 136 054).
sulphinic acid (Vol. 8, p. 9), thus preventing [1,3] rearrangement, to label allylic
positions with deuterium; (+)-p-menth-1-ene may be pentadeuteriated without
r a c e m i ~ a t i o nA. ~previous
~~ report (Vol. 6, p. 29) on the Diels-Alder addition of
butadiene to (-)-carvone [(4R)-(18)]did not mention the favourable influence of
added A1Cl3 on the reaction yield nor that in its presence the only minor product
corresponds to bringing the side-chain double bond of the major adduct into
conjugation with the carbonyl group; the full paper has been published.499The
structure of the a -phellandrene-maleic anhydride adduct has been confirmedSoo
and the retro-Diels-Alder reaction of limonene using a CO, laser has been
reported again (Vol. 3, p. 31).501Other observations relating to the fate of the
a-terpineyl cation in 85% phosphoric acid are that a-terpineol and p-menth-l-
en-4-01 give rise to no limonene but yield almost identical mixtures of hydro-
carbons which may be derived from (67) or rearranged carbocations derivable
therefrom.388In contrast, the rearrangement of 0-menthyl methylthiocarbamate
by BF,,OEt, to cis- and trans-S-p-menthan-8-yl methylthiocarbamates may
result from the predominant rearrangement of dihydro-(67) to the dihydro-cu-
terpineyl cation.5n2Other related papers report the generation of (141) from
limonene in S02FC1-FS03H and its collapse to a-terpinene, a-phellandrene,
and /3-phe1landrene5O3(although this route does not appear to be followed in
85% phosphoric further carbonium ion transformations (cf.Vol. 7, p. 31)
over salicylic acid (a-phellandrene, p -phellandrene, and a - t e ~ p i n e n e ) , and
~ ' ~ the
acid-catalysed ethanolysis of allylic alcohols (e.g. the p-menth-2-en-1-01s and the
p i p e r i t o l ~ ) .Carvomenthone
~~~ (135) and carvenone (142) undergo dehy-
drogenation and rearrangement in SbF,-HF to yield (143)-(146) whereas
menthone yields piperitone (147); the results can be rationalized on the basis of
initial dication formation with protolysis occurring at a tertiary C-H bond p to a
protonated carbonyl group.5o6
Photo-oxidation of limonene in pyridine in the presence of U02(0Ac)2,2H20
proceeds by anti-Markovnikoff addition of hydroxy-radical followed by reaction
with molecular oxygen to yield ( 148)?07The identical photoreactions of methanol
with pulegone (21) in the presence of TiCl, and U02C12(Vol. 7, p. 8) have now
been reported in Sensitized photoaddition of methanol to carvone (18),508
498 D. Masilarnani and M. M. Rogic, J. Amer. Chem. SOC.,1978,100,4634.Acloselyrelateddeuteriation

procedure using the reversible ene reaction of TsNS0216 has been used to produce [lO-ZH,]-(-)-
carvone from (4R)-(-)-(18).
499 T. Harayarna, H . Cho, and Y. Inubushi, Chem. and Pharm. Bull. (Japan), 1977,25, 2273.
500 B. Singararn and J. Verghese, J. Indian Chem. SOC.,1977, 54, 630.
501 D . Garcia and P. M. Keehn, 175th A.C.S. Meeting, Annaheim, California, March 1978, Abstracts
ORGN, No. 109.
502 Y. Kinoshita, M. Misaka, S. Kubota, and H. Ishikawa, Agric. and Biol. Chem. (Japan), 1977, 41,
2357.
503 I. I. Bardyshev, V. A . Barkhash, Z. V. Dubovenko, and V. I. Lysenkov, Zhur. org. Khim., 1978,14,
1 1 10.
504 I. I. Bardyshev, L. A. Popova, E. F. Buinova, and B. G. Udarov, Vestsi Akad. Nauuk belarusk.
S.S.R., Ser. khim. Navuk, 1977, (3), 58 (Chem. Abs., 1977, 87, 135 988); L. A . Popova, Tezisy
Dokl. - Resp. Konf. Molodykh Uch. - Khim., Znd, 1977, 1, 58 (Chem. Abs., 1978, 89,90 226).
505 J. Taskinen, Internat. Flavours Food Addit., 1976, 7 , 235; see also ref. 573.
506 R. Jacquesy and J.-F. Patoiseau, Bull. SOC.chim. France, 1978, 2 5 5 .
507 E. Murayarna and T. Sato, Tetrahedron Letters, 1977, 4079.
508 B. Fraser-Reid, N. L. Holder, D . R. Hicks, and D. L. Walker, Canad. J. Chem., 1977, 55, 3978.
Monoterpenoids 55
(145) (146) (147) ( 148)

a further investigation of menthone photochemical transformation^,^^^ and non-
selective proton transfer from p - cymene as the radical-cation half of an e x ~ i p l e x ~ ~ '
are described in other papers.
The oxidation of a-terpinene to ascaridole (Vol. 7, p. 6) has been examined
further; quantitative conversion occurs either photochemically using (hv-02-
SnC14-CH2C12,-90 "C) or in the dark using (02-liquid SO2, -70 "C) compared
with Lewis acid-catalysed dark reactions which are less efficient (e.g. 0,-VOC1,-
CH2C12,67O/0).~"Oxymercuration-demercuration of CY -terpinene yields (149;
X = OH; cis :truns/3 : 1); similarly a-phellandrene yields predominantly trans-
carvotanacetol (150) with minor amounts of (149; X = H; cis : truns/7 : l),
whereas p-phellandrene yields predominantly (149; X = H; cis : trans/54 : 19),
together with some p-menthane-1,3-diols in both The aerial oxidation of
some p-menthadienes and p-cymene in dipolar aprotic solvents to p -methyl-
acetophenone or 2-( p-methylphenyl)propan-2-01 has been Lead
tetra-acetate oxidation of methoxy-substituted p -cymenes occurs predominantly
c" c"" poH

at the C-1 methyl group (e.g. to yield 4-isopropyl-3-methoxybenzyl
peracid oxidation of menthylimines yields diastereoisomeric oxaziridines in high
l ~ ~cis- and trans-isocarveols [cis- and trans-(15 l)], which are
optical ~ i e 1 d s .The
(149) (150) (151)

'09 R. K. Baslas, Indian Perfumer, 1976, 20, 131.
'lo P. J. Wagner and A. E. Puchalski, J. Amer. Chem. SOC.,1978,100,5948.
'11 R. K. Haynes, Austral. J. Chem., 1978, 31, 131.
512 M. Bambagiotti A., S. A. Coran, and F. Vincieri, Rivista Ztal.,Essenze-Profumi,Piunte Offic.,Aromi,
Saponi, Cosmet., Aerosol., 1978,60, 83.
513 H. Iwamuro, T. Ohshio, and Y. Matsubara, Nippon Kaguku Kuishi, 1978,909.
'14 V. V. Dhekne and A. S. Rao, Synth. Comm., 1978,8,135.
obtained most efficiently from the respective limonene-1,2-epoxides by rear-

rangement using lithium di-isopropylamide, are rearranged allylically to perilla
alcohol [(103; R = CH20H);up to 84%] uia PBr3 bromination, with rearrange-
ment, and hydrolysis, as a viable alternative to the inefficient thermal rearrange-
ment of derived esters and the complete absence of direct rearrangement of the
parent alcohols. The corresponding perillaldehyde (103; R = CHO) may be
obtained from [cis- and trans-(15l)]by oxidation-isomerization or directly from
perillyl bromide (103; R = CH,Br) by treatment with 2-nitropropane and base;
synthetically, trans-( 151) is the favoured starting material in these trans-
f o r m a t i o n ~ .Catalysed
~’~ rearrangements of limonene- 1,2-epoxide by platinum-
group metals may yield carvenone (142) p r e d ~ m i n a n t l y ’although
~~ a more
effective synthesis (92%) utilizes an exchange resin;517another exchange resin
catalyses dihydrocarvone production (82’/0).’~~ Reaction of both limonene-1,2-
e p o x i d e ~ ’and
~ ~ the diepoxide519with amines518*s19 and with azidesl’ have been
reported and a further paper on epoxide rearrangement over solid acids and bases
(cf. Vol. 8, p. 43) concerns the corresponding saturated carvomenthene epox-
ide.s20 Lead tetra-acetate oxidation of the 4’-phenylsemicarbazone of 1,6-
epoxycarvone yields the oxadiazoline (152) which is thermolysed readily to
3-i~opropenylhept-5-ynal.~~’ Reductive cyclization of pulegone hydrochloride to
(15 3) using Zn-HC1-Ac20 occurs uia pulegone (2 l).s22 Sodium borohydride
reduction of enones [e.g. carvone (18), pulegone (21), piperitone (147)] in the
presence of the lanthanide CeC13,6H20 or E I - ( N O ~ ) ~ , ~proceedsH ~ O almost
exclusively by 1,2-addition to yield allylic alcohol^;^^^ further data on complex
metal hydride reduction of carvone (18)and dihydrocarvone have been published
(cf. Vol. 1, p. 30; Vol. 7, p. 7).524The reductive dimerization of (+)-pulegone
[(lR)-(21)]has resulted in a number of recent papers (Vol. 2, p. 21; Vol. 4, p. 36;
Vol. 6, p. 31); another now provides chemical evidence supporting the absolute
configuration of the two series of ketols [e.g. (154)] and derivatives [uiz.allo- and
iso- (cis- and trans-C-4’-methyl and C-2/C-3 respectively)] (cf.Vol. 7, p. 29).525
515
Y. Bessikre and F. Derguini-BoumCchal, J. Chem. Res. (S), 1977, 304. A more efficient synthesis
(77%) of the cis-(151) only has been reported from the trans-l,2-epoxylimonene (Vol. 8, p. 43; ref.
384); last year’s Report erroneously implies otherwise. Line 11 should read (in part) ‘some expected
arornatization is observed’ and not ‘the expected aromatization is observed’. For related work in the
pinane series, see ref. 648.
’I6 T. Kurata, Yukagaku, 1978,27, 226.
’I7 N. E. Kologrivova, Z. V. Kamaeva, and L. A. Kheifits, Zhur. Vsesoyuz. Khim. obshch. im. D.I.
Mendeleeva, 1977,22, 223 (Chem. Abs., 1977,87, 135 966).
”’ S. A. Kozhin, V. V. Zaitsev, and B. I. Ionin, J. Gen. Chem. (U.S.S.R.), 1978,48,177; the aminolysis
of derived hydroxytosylates is also discussed.
’19 L. A. Mukhamedova, F. G. Nasybullina, and M. 1. Kudryavtseva, Bull. Acad. Sci. U.S.S.R., Div.
Chem. Sci.,1977,26, 191 1.
520 K. Arata, S. Akutagawa, and K. Tanabe, Bull. Chem. SOC. Japan, 1978, 51,2289.
”’ G. A. MacAlpine and J. Warkentin, Canad. J. Chem., 1978,56, 308.
”’ E. Cros, I. Elphimoff-Felkin, and P. Sarda, Compt. rend., 1978, 286, C, 261.
523 J.-L. Luche, L. Rodriguez-Hahn, and P. Crabbt, J.C.S. Chem. Comm., 1978,601. The paper refers
to carvone (18) reduction but the formulae depicted correspond to carvotanacetone and carvo-
tanacetol. For additional complex metal hydride reduction data, see Vol. 1, p. 39, ref. 155.
’24 H. Rothbacher and F. Suteu, Chem.-Ztg., 1978,102, 61.
”’ E. FornC and J. Pascual, J.C.S. Perkin I, 1978, 288. It appears also that the X-ray structures of the
allo-ketol, bishydropulegone, and the related dehydrobispulegone have been determined by
D. Rogers et af.but never published (D. Rogers, personal communication; see also this reference and
Vol. 7, p. 29, ref. 288).
Monoterpenoids 57
(152) (153) (154)

Another use (cf. Vol. 5, p. 24) of chiral Rh(cod)(cyclohexylmethyl-o-anisyl-
phosphine),BF, for asymmetric homogeneous hydrogenation is the highly selec-
tive reduction of piperitenone (155) to (-)-pulegone [(lS)-(21)] in up to 33%
enantiomeric excess; slight modification of the ligand, however, produces the
unusual observation of solvent-dependent selectivity to produce piperitone (147)
p r e d ~ m i n a n t l y Selective
.~~~ reductions of carvone (18) to dihydrocarvone using
(CoC12,6H20-dimethylglyoxime)527 and of perillaldehyde (103; R = CHO) to
shisool [(156; R = CH20H); cis: transll : 1 using Li-NH3-propan-2-01], shisoal
[(156; R = CHO); cis : truns/3 : 1 using Li-NH3-propan-2-01 with inverse addi-
R
I
(155) (156)
tion], or p-menthan-7-01 [large-scale reaction (!) using Li-NH3-propan-2-01]
have been reported.s28Further papers on p-cymene reduction to y-terpinene as
the major product (using or calcium in liquid
ammonia529b)have been published.
Additional data on the thermal rearrangement of endo- cineole halohydrins
and dihalides to halopinol derivatives (Vol. 8,p. 44) have been rep~rted.'~'In
further attempts to synthesize 2,3-didehydro-l,8-~ineole, nitrosation of the
endo- and exo-aminocineoles (157) results in a stereosyecificity not observed
with dehydration of the corresponding alcohols (Vol. 8,p. 41); endo-(157) yields
(158) and exo-(157) yields (159). The successful route to 2,3-didehydro-1,8-
cineole involves reduction of 2-hydroxyimino- 1,8-cineole with sodium bis-(2-
methoxyethoxy)aluminium hydride to the corresponding aziridine followed by
nitrosation; interestingly, LiAlH, reduction of 2-hydroxyimino-l,8-cineoleis the
most efficient route for the synthesis of ( 160).531" Bamford-Stevens reaction,
s26 J. Solodar, J. Org. Chem., 1978, 43, 1787.

s27 W. J. Ehmann, U.S.P. 4 020 108 (Chem. Abs., 1977,87, 136 044). For earlier reports of selective
hydrogenation of carvone (18), see Vol. 4, p. 32; Vol. 7, p. 32.
528 R. Murphy and R. Prager, Austral. J. Chem., 1978,31, 1629.
s29 V. V. Bazyl'chik and P. I. Fedorov, ( a )Zhur. obshchei Khim., 1978, 48, 674; ( b ) J. Appl. Chem.
(U.S.S.R.), 1977,50, 1825; cf. Vol. 8, p. 44.
530 J. Wolinsky, J. H. Thorstenson, and M. K. Vogel, J. Org. Chem., 1978, 43, 740.
s31 F. Bondavalli, A. Ranise, P. Schenone, and S. Lanteri, ( a )J.C.S. Perkin I, 1978, 804; ( b )personal
communication.
under protic conditions, of the corresponding (+)-1,3,3-trimethy1-2-oxabicy-

clo[2,2,2]octan-6-one tosylhydrazone yields (159) plus some anhydro-( 159) and
pinol. Under aprotic conditions the reaction is more complex, yielding substantial
amounts of carbene-coupling Syntheses of alcohols and ketones
derived from pinol have been r e p ~ r t e d . ’ ~ *
Other papers related to p -menthanes concern the addition of chlorosulphonyl
isocyanate to the exocyclic double bond of l i m ~ n e n ephenylselenenyl
,~~~ chloride
addition to (Y -terpine01,~~’cyclization of a -phenylselenocitronellal,223cyclo-
addition of methylthiomaleic anhydride to (Y - ~ h e l l a n d r e n e ,HNCO
~ ~ ~ addi-
tion to a- and P-pinene (but not limonene) to yield a-terpineyl i ~ o c y a n a t e , ~ ~ ’
formation of (Y -terpineol n i t r o ~ o b r o m i d e , ’stereochemical
~~ assignment of
(+)-dihydrocarvone oxime and (-)-carvoxime [of known X-ray structure
( !)57b*c],537 (-)-carvotanacetone synthesis via dehydrohalogenation of p-menth-
1-ene nitros~chloride,’~’menthol hydrosilylation in molten dodecylammonium
p r ~ p i o n a t e , ’catalysed
~~ rearrangement of shisool (156; R = CH20H) into p-
menth-3-en-7-01,’~’ arylation of p - ~ y m e n e , ~a ~reassignment
’ of the structure for
the (-)-menthone-benzylideneacetophenone condensation reaction
of limonene with recoil tritium atoms (to yield products from tritium incorpora-
tion and also radiolytic processes),542 2-isopropyl-5-methylphenoxyacetato-
copper(I1) c~mplexes,’~’and copper(I1) chelate compounds with enamino-
ketones derived from (-)- hydroxyme thylenecarvone.544
o-Menthanes.-Bohlmann has isolated (161) and (162) from Piqueria tri-

ner~ia.~ The
~ ’ reduction of o -cymol with calcium,546 or
in liquid ammonia in the presence of alcohols to yield o-mentha-1,4-diene (163)
predominantly (together with o -mentha-3,6-diene, o -menth-1-ene, o-menth-2-
532 A. Siemieniuk, D. Mrozinska, and K. Piatkowski, Polish J. Chem., 1978, 52,727.
s33 G. Mehta, D. N. Dhar, and S. C. Suri, Indian J. Chem., 1978,16B, 87.
s34 B. M. Trost and G. Lunn, J. Amer. Chem. SOC.,1977,99,7079.
535 T. Lesiak and W. Forys, Polish J. Chem., 1978, 52, 927.
536 C. P. Mathew and J. Verghese, J. Indian Chem. Soc., 1977,54,847.
537 B. Singaram and J. Verghese, Indian J. Chem., 1977,15B, 854.
s38 B. Singaram, G. N. Saraswathi, and J. Verghese, Indian J. Chem., 1977,15B, 908.
539 J. Boyer, R. J. P. Corriu, R. Perz, and C. Reye, J. Organometallic Chem., 1978, 145, C31.
s40 G. Vernin, C. Siv, and J. Metzger, Synthesis, 1977, 691.
541 G. L. Buchanan, Org. Magn. Resonance, 1978,11,45.
s42 A. Cecchi, N. Taccetti, M. Bambagiotti A., S. A. Coran, and F. F. Vincieri, Radiochim. Acta, 1976,
23, 113.
543 J. Kratsmar-Smogrovic and V. Seressova, Chem. Zvesri, 1978, 32, 5 .
’*‘ G. V. Panova, V. M. Potapov, and N. K. Vikulova, Zhur. obshcheiKhim., 1978,48, 1611.
’‘’ F. Bohlmann and A. Suwita, Phytochemistry, 1978,17,560; (162) may have been reported already
(Vol. 1, p. 35) although no direct comparison has been reported.
546 V. V. Bazyl’chik, P. I. Fedorov, and N. M. Ryabushikina, Zhur. org. Khim., 1978,14, 969.
Monoterpenoids 59
ene, and o- menth-6-ene) and the dehydration of cis- and trans-o-menthan-8-01s

have been Other papers describing transformations involving the
o -menthane carbon skeleton concern the tris(triphenylphosphine)ruthenium(II)
dichloride-catalysedrearrangement of ally1 cyclohex-1-enylmethyl ether and the
Claisen rearrangement to (164; R = CHO)548and oxyrnercuration-reduction of
(164; R = Me).549
(161) (162) (163) (164)
rn-Menthanes.-The ester (165; R = COPr’) has been isolated from Eupatorium

species471cand from Senecio spe~ies,’’~ which have also yielded the ether (165;
R = Me). I3CN.m.r. data have been recorded for (166).551The conformations of
five rn -menthenols have been investigated using their i.r. hydroxy-group absorp-
t i ~ nIn. attempts553
~ ~ ~ to rearrange 2a,3a-epoxycarane to (65)384by cyclopropyl-
assisted epoxide ring opening in the presence of ZnBr2, rearrangement occurred
predominantly to the non-naturally occurring rn -menthenone (167) and p -
cyrnene. No (65) was i~olated.”~ Catalytic dehydration of trans-rn-menthan-8-01
[to trans-rn-menth-8-ene/rn -menth-3(8)-ene or to rn -menth-2-ene/rn -menth-
3-ene pred~rninantly]”~and the hydration of five appropriately substituted
rn -menthenols to similar proportions of cis- and trans-sylveterpin ( 168)555have
been examined. Much of the work on sylvestrene nitrosochloride trans-
f o r m a t i o n ~represents
~~~ minor modifications of work reported previously (Vol.
8, p. 46).
547 V. V. Bazyl’chik and E. A. Ionova, Zhur. org. Khim., 1978,14,538.

548 J. M.Reuter and R. G. Salomon, J. Org. Chem., 1977,42,3360.
549 Y.Senda, S.-I. Kamiyama, and S. Imaizumi, J.C.S. Perkin I, 1978,530.
550
F. Bohlmann, K.-H. Knoll, C. Zdero, P. K. Mahanta, M. Grenz, A. Suwita, D. Ehlers, N. L. Van,
W.-R. Abraham, and A. A. Natu, Phytochemistry, 1977, 16, 965;this paper was inadvertently
omitted from last year’s Report. This Reporter is unaware of any previous reports of naturally
occurring (165;R = COPr’).
5s 1
K. Bachmann, Ph.D. Thesis, University of Zurich, 1977.For the X-ray structure of (166),see ref.
62a.
552
I. A. Shingel and I. V. Zen’ko, Vestsi Akad. Navuk belarusk. S.S.R., Ser. khim. Navuk, 1977,(5),99.
553
B.C. Clark, jun., T. C. Chafin, P. L. Lee, and G. L. K. Hunter, J. Org. Chem., 1978,43,519.
554
G . V. Deshchits and I. I. Bardyshev, Vestsi Akad. Navuk belarusk. S.S.R., Ser. khim. Navuk, 1977,
(4),111.
555
I. I. Bardyshev, I. V. Zen’ko, G. I. Voitekhovskaya, and N. G. Zimina, Vestsi Akad. Navuk belarusk.
S.S.R., Ser. khim. Navuk, 1977,(5),122.
556
B. Singaram, G. N. Saraswathi, and J. Verghese, Indian J. Chem., 1977,15B,903.
Tetramethylcyc1ohexanes.-Aldehydo-esters (169; R = OAc, OH, or H) related

to isoferulol have been isolated from Piqueria t r i n e r ~ i uand
~ ~the
~ structures of the
furocoumarin ethers iselin and iliensin (Vol. 7, p. 35) have been revised and
shown by synthesis to be derivatives of P-cyclolavandulol (170).557Cocker et ul.
have examined the sensitized photo-oxygenation and peracid oxidation of a -

pyronene (171) together with reductive and other manipulations of the oxidation
products, with similar observations (after allowing for changed diene locus) to
those made earlier for similar reactions in the P-pyronene series (Vol. 5, p. 28)
except that PhC0,H-Et,O oxidation yields the less-substituted epoxide (172)
presumably because in this case steric factors outweigh electronic
Two-phase chromic acid oxidation of /3 -pyronene has been re-examined at lower
temperatures than used by Cocker et al. (Vol. 5, p. 28) and has allowed the
isolation of four additional products; unfortunately yields for them and for related
cy -pyronene oxidation products have not been In 85% phosphoric
acid, protonation of the isopropylidene double bond competes (-13%) with
ionization of geraniol (but not nerol or linalool) resulting in cyclization to
(173);388the formation of (174) as a minor product in the aqueous citric
acid-catalysed cyclization of geranyl acetate may involve similar protonation and

ring closure with syn-addition of a molecule of water at C-3.389The telomer,
N,N-diethylnerylamine, has been cyclized using BF3,Et20-HOAc to
the mixture N,N -die thyl- ( a-cyclogeran y1)amine :N,N-die thyl- ( y -cyclogeranyl)-
amine/39 :60.560 Further papers of interest in this section concern allyl-
~ ~ and triols derived from P -cyclo~itral,~~’
b ~ r a t i o n , ’ diols sensitized photo-
oxygenation of the ethyl ester of a-safranic acid followed by reduction and
557 S. K. Paknikar, J. Veeravalli, and J. K. Kirtany, Experientia, 1978, 34, 553.
”* W. Cocker, K. J. Crowley, and K. Srinivasan, J.C.S. Perkin I, 1978, 159.
’59 J. de Pascual Teresa, I. Sanchez Bellido, M. R. Alberdi Albistegui, A . San Feliciano, and M. Grande
Benito, Anales de Quim., 1978,74,470.
J. Tanaka, Jap. P. 48 642/1977 (Chem.Abs., 1977,87,136 049). For further transformations of this
telomer, see ref. 359.
D. Behr, I. Wahioerg, and C. R. Enzell, Acra Chem. Scand., 1977, B31,793.
Monoterpenoids 61
~ e a r r a n g e m e n t , ~and
~ ~ alkylation of l-(phenylsulphonylmethyl)-2,6,6-tri-
methylcyclohexa- 1,3-diene.563
Dimethylethylcyc1ohexanes.-The two aldehydic and one alcoholic dimethyl-
ethylcyclohexane components of the boll weevil sex pheromone have been
synthesized efficiently via ZnCl,-catalysed addition of ethyl vinyl ether to the
ethyl acetal of 3,3-dimethylcyclohexanone.564
Cyc1oheptanes.-'H N.m.r. spectral data for beryllium bis-(a -iso-
or
propyltropolonate) have been The full paper on Noyori's syntheses
of nezukone, a-thujaplicin, and p-thujaplicin or hinokitiol (175; R = Pr') has
been Compound (175; R = Pr') has also been synthesized according
to Scheme 4.567 Other syntheses of p-thujaplicin (175; R=Pr') have been
o n o M e _ o+ iii
__*
\+
N N
Me Me Me
/" C0,Me
'06 -
R vi-viii -
C0,Me
(175) R=Pr'
Reagents: i, Pr'MgBr; ii, m-ClC6H4C03H-CH2C12; iii, CHz=CHC02Me-THF; iv, MeI; v,
NaHC03-HzO; vi, 10% aq. HCI; vii, IN aq. KOH; viii, copper chromite-quinoline,
230 "C
Scheme 4
reported. One of them involves reaction of the tricarbonyliron complex (176)

with 2-diazopropane to yield the corresponding pyrazoline which readily loses
nitrogen and undergoes alkaline P-ketone cleavage to yield (177); decom-
Fe(CO),
(176) (177)
562 R. Kaiser and D. Lamparsky, Helv. Chim. Acta, 1978,61, 373.
563 S. Torii, K. Uneyama, and I. Kawahara, Bull. Chem. Suc. Japan, 1978,51,949.
564 J. P. de Souza and A. M. R. Goncalves, J. Org. Chem., 1978, 43, 2068.
565 A. Gryff-Keller and J. Terpinski, Roczniki Chem., 1977, 51, 2139.

566 H. Takaya, Y. Hayakawa, S. Makino, and R. Noyori, J. Amer. Chem. Soc., ( a ) 1978, 100, 1778;
( 6 ) ibid., 1978,100, 1765. See also ref. 259. For the earlier communication see Vol. 6, p. 33.
"' Y. Tamura, T. Saito, H. Kiyokawa, L.-C. Chen, and H. Ishibashi, TetrahedronLetters, 1977,4075.
plexation, base conjugation, and introduction of the hydroxy-group by Noyori’s

method566 transforms (177) into (175; R = Pri).568Another synthesis utilizes
lithium-ammonia reduction of triethylsilyl 3-isopropylphenyl ether to (178)
followed by anticipated dichlorocyclopropanation, hydrolysis, and epoxidation to
give (179) which yields (175; R = P i ) on acid-catalysed elimination and hydro-
l ~ s i s . ’Essentially
~~ the same scheme from triethylsilyl 4-isopropylphenyl ether
yields y-thujaplicin, although in an attempted synthesis of a -thujaplicin
dichlorocyclopropanation of the dihydroaromatic silyl ether corresponding to
(178) failed, presumably for steric reasons.569P-Dolabrin (175; R = CHMe=
CH2) has also been synthesized568from (177) via oxidative tropone formation
prior to decomplexation and known566hydroxylation; a second synthesis involves
reaction of isopropylmagnesium bromide with (180; X = 0 , Y = OMe,OMe) and
subsequent dehydration-deacetalization to (180; X = CMe2, Y = 0),the enolate
of which undergoes electrocyclic ring opening, silylation, oxidation, and hydro-

lysis to (175; R=CHMe=CH2).570 Further (cf. Vol. 8, p. 48) on
karahanaenone (27; X = 0) formation by Zn-Cu couple dehalogenation of
1,3-dibrom0-3-methylbutan-2-onein the presence of isoprene shows an unusual
reversal of selectivity on changing the solvent polarity, although yields remain
low. In acetonitrile, karahanaenone (27; X = 0)is now the minor cycloheptenone
and substituted cyclopentanone formation is when zinc is replaced
by sodium iodide, formation of these products is almost completely suppressed in
favour of substituted furan formation - see p. 77.s71b The charge distributions of
protonated eucarvone and its boron trihalide adducts have been examined (there
is more dienylic positive charge in the former)572aand the photoisomerization of
the latter has been shown to be qualitatively similar to results with the former
(Vol. 2, p. 36) although synthetic utility is limited because car-2-en-4-one,BX3
adducts readily yield carvacrol and carvone (
8 Bicyclic Monoterpenoids
Bicyclo[3,1,O]hexanes.-Acid-catalysed ethanolysis (80% EtOH) of cis-
sabinene hydrate (28) and its trans -isomer (of unspecified chiralities) yields 30%
of p-menth-1-en-4-01;~’~ it would be of interest to know its optical purity in view
of the reports that (+)-trans-sabinene hydrate may be isomerized to p-menth-l-
568 M. Franck-Neumann, F. Brion, and D. Martina, Tetrahedron Letters, 1978, 5033.

569 T. L. Macdonald, J. Org. Chem., 1978,43, 3621.
570 D. A. Evans, D. J. Hart, and P. M. Koelsch, J. Amer. Chem. SOC.,1978, 100,4593.
571 H. M. R. Hoffmann and R. Chidgey, Tetrahedron Letters, ( a ) 1978,85; (b) 1978, 1001.
572 R. F. Childs and Y.-C. Hor, Canad. J. Chem., ( a ) 1977,55, 3495; (b) 1977, 55, 3501.
Monoterpenoids 63
en-4-01 (4R :4S/3 : 7)573and acid-catalysed hydration of (+)-sabinene yields

(+)-p-menth-l-en-4-01 stereospecifically (Vol. 3, p. 57). Attempts to use known
thujone chemistry in synthesizing insect juvenile hormone analogues have been
Umbellulone (18 l), together with the isomeric 2,4-transposed
ketone, has been obtained by treating (182) with lithium dimethylcuprate and
reaction of the enol lactones derived from the resultant keto-acid mixture with
diethylmethanephosphonate anion.575
Bicyclo[2,2,l]heptanes.-Last year's Report incorrectly identifies vulgarole

[Vol. 8, p. 49, line 21, formula (202; R = Ac) should be (208; R = Ac)]. A review
of interest to this section concerns oxidation of bicyclic hydrocarbons using
oxygen, hydroperoxides, peracids, and hydrogen The full paper on
nojigiku alcohol has appeared;577the isolation of a new compound (132) has been
referred to already.470
Recent X-ray crystal structure determinations have been reported earlier (see
p. 8). A number of n.m.r. papers have been published. The 'H n.m.r. assignment
of camphorimide has been made using [ E ~ ( d p m ) ~ ]and ' ~ ~long-range proton
coupling constants have been measured for 3-endo,4-disubstituted
the influence of substituents on 13C carbonyl chemical shifts in 4-substituted
camphorquinones has been inve~tigated.~'~ A comparison of 'H n.m.r. chemical
shift and relaxation rate data for complexes of (-)-borne01 with lanthanide shift
reagents containing the ions Eu3+,Pr3+, La3+, and Gd3+ has revealed that the
geometrical data for Gd3+ compiexes are incompatible with data from Eu3+or
Pr3+c ~ r n p l e x e s ; ~an' ~examination of 'H and 13Cn.m.r. chemical shifts and signal
broadening induced by four [ L n ( d ~ mJ )shift ~ reagents indicates that the metal
binds to two sites on the carbonyl group of camphor.582The 13C n.m.r. signals
573
D. Karasawa, Shinshu Daigaku Nogakubu Kiyo, 1977, 14, 119 [Chem. Abs., 1978, 89, 24 543
incorrectly refers to (+)-trans-sabinene]. The enantiomeric composition was determined using
tris-[3-trifluoroacetyl-(+)-camphorato]eur~pium(~~~).
574
J. P. Kutney, J. Balsevich, R. Carruthers, A. Markus, M. J. McGrath, R. N. Young, and B. R. Worth,
Bioorg. Chem., 1978,7,289.
575
S. Benayache, C. FrCjaville, R. Jullien, and M. Wanat, Rivista Ital. Essenze-Profumi, Piante Offic.,
Aromi, Saponi, Comet., Aerosol., 1978, 60, 118.
576
E. A. Lazurin, V. V. Voronenkov, and Yu.G . Osokin, Russ. Chem. Rev., 1977,46, 915.
577
Y. Uchio, Bull. Chem. SOC. Japan, 1978,51,2342;see Vol. 6, p. 35 for the communication and Vol.
7, p. 38 for a synthesis.
578
S. M. Verma and R. Prasad, Indian J. Chem., 1977,15B, 742.
579
F. C. Brown, R. K. Fraser, R. W. Jemison, D. G. Morris, A. M. Murray, and J. D. Stephen, Austral. J.
Chem., 1978, 31, 695; for a related paper, see ref. 613a.
580
F. C. Brown, D. G . Morris, and A. M. Murray, Tetrahedron, 1978, 34, 1845; variations in i.r.
stretching frequencies are also reported.
581
D. H. Welti, M. Linder, and R. R. Ernst, J. Amer. Chem. SOC.,1978,100,403.
582
B. H. S. LiCnard and A. J. Thompson, J.C.S. Perkin ZZ, 1977, 1390.
have been assigned for (-)-2-endo -dimethylphosphono-2-exo-thio-

methylcamphane and a Karplus-type function derived for vicinal coupling
constants in p h o ~ p h o n a t e s .Further
~ ~ ~ papers concern a I3C n.m.r. study of the
two pinacols derived from ~ a m p h e n i l o n e an , ~ ~examination
~ of a -+ S effects
produced by C-1 and C-4 triflate and ethoxy-groups in ~ a m p h e n e , ~and ~ ’ ‘H
n.m.r. and 13C n.m.r. assignments of a series of 2-aryl-177,7-tri-
methylbicyclo[2,2,l]hept-2-ylcations derived from the corresponding exo -alco-
h o l ~ Mass . ~ ~ spectral
~ fragmentations of chlorinated bornanes have been
examined587 and further investigation (Vol. 5 , p. 3 l), using deuteriated
compounds, of the cis-1,2-elimination of water from the molecular ions of
borneol and isoborneol has shown that it is triggered by initial ring cleavage; the
experimental results are inconsistent with an earlier proposal (Vol. 3, p. 59)
involving non-classical carbonium ions.476C.d. data on Schiff -base condensation
products of a c e t y l ~ a m p h o rhave ~ ~ ~ been published as well as for 9,9,9-tri-
d e u t e r i o ~ a m p h o rfor
, ~ ~a ~number of fenchone- and camphor-related ketones,590
and for electron donor-acceptor charge-complexes between iodine and camphor
and iodine and c a m p h ~ r q u i n o n e . ~( ~ - )’ - B ~ r n e o l and
~ ~ ~(+)-camphor593 have
been the subjects of theoretical c.d. studies. E.s.r. studies of nitryl radical mobility
in camphor,594 of silyl, stannyl, and plumbyl radical addition to
c a m p h o r q ~ i n o n eand
, ~ ~of~ cation-radicals generated from dehydrocamphor and
r ~ ~ ~been published. Other papers of a physical nature
d e h y d r o e p i ~ a m p h o have
concern (&)-campheneself-diff u ~ i o nelectrical , ~ ~ ~ conductivity of plastic crystals
of (*)-carnphoric anhydride, (*)-camphorquinone, and ( f ) - c a m p h o r ~ x i m e , ~ ~ ~
partition of isobornyl acetate between phenol and water,599and the synthesis,
resolution, and olefactory properties of the exo- and endo-4-(2’-bornyl)-2-
methylcyclohexanones and of the exo- and endo -2-rnethyl-4-(5’,S76’-exo-tri-
methyl-2’-norbornyl)cyclohexanones.600
Pyrolysis of exo-(183; X = CD2NOMe2),601a which is obtained, without rear-
rangement, from optically pure (+)-isocamphenilanic acid of absolute
583 J. Thiem and B. Meyer, Org. Magn. Resonance, 1978, 11, 50.
584 J. B. Stothers and K. C. Teo, Org. Magn. Resonance, 1977, 9, 712.
585 A. Garcia Martinez and M. Gornez Marin, Anales de Quim., 1978,74, 339.
586 J. M. Coxon, P. J. Steel, J. M. Coddington,I. D. Rae,andA. J. Jones,Austral. J. Chem.,(a)1978,31,
1223; ( 6 )for related work, see ibid., 1977,30,2741. See also Vol. 6, p. 37 and later discussion in this
section.
587 H. Parlar, S. Nitz, A. Michna, and F. Korte, Z. Naturforsch., 1978, 33b, 915.
588 H. P. Jensen, Acta Chem. Scand., 1978, A32, 149.
589 W. L. Meyer, A. P. h b o , E. E. Ernstbrunner, M. R. Giddings, and J. Hudec, Tetrahedron Letters,
1978,1771.
590 D. N. Kirk, J.C.S. Perkin I, 1977, 2122.
591 H. G. Brittain and F. S. Richardson, J.C.S. Faraday II, 1978,74,115 1; for related work, see ref. 118.
592 P. A. Snyder and W. C. Johnson, jun., J. Amer. Chem. Soc., 1978, 100,2939.
s93 J. Texter and E. S. Stevens, J. Chem. Phys., 1978,69, 1680.
594 S. T. Kirillov and V. B. Stryukov, Russ. J. Phys. Chem., 1976, 50, 1746.
595 A. Hudson, R. A. Jackson, and N. P. C. Simmons, J.C.S. Perkin II, 1977, 1633.
596
J . Eloranta, E. Salo, and P. Malkonen, Finn. Chem. Letters, 1977, 217.
597 N. T. Corke, N. C. Lockhart, R. S. Narang, and J. N. Sherwood, Mol. Crystals Liquid Crystals, 1978,
44,45.
598 J. Swiatkiewicz and K. Pigon, Acta Phys. Polon., 1978, A53, 165 (Chem. Abs., 1978,89, 59 962).
599 J. R. Alvarez Gonzalez and J . J. Niela Nieto, Anales de Quim., 1978, 74, 326.
6oo E. T. Theimer, T. Yoshida, and E. M. Klaiber, J. Agric. Food Chem., 1977,25, 1168.
‘” G. Buchbauer and H. Koch, ( a ) Chem. Ber., 1978, 111, 2533; ( h ) ibid., p. 2527.
Monoterpenoids 65
configuration [exo-(183; X = C02H)],yields [8,8-2H2]-(-)-camphene (184; X =

H,H; Y = CD2);601a in the corresponding non-deuteriated series, (-)-camphene
(184;X = H,H; Y = CH2)with [a]&!= -1 19.11' (benzene, c = 2.33)wasobtained
thus providing unambiguous proof of its A synthesis of [3-exo -
2Hl]camphor has been reported earlier.259The full paper on (+)-camphor
synthesis by (+)-dihydrocarvone pyrolysis has appeared.602Another application
of Nakai's 1,2-carbonyl-transposition scheme (cf. Scheme 3) is the conversion of
camphor into epicamphor (46% yield).485Treatment of 3-endo- (p-t-butyl-
pheny1)selenocamphorwith H 2 0 2under mild conditions yields camphorquinone
(65'/0)~~~which has been used in a synthesis of tricyclenone (185) via Bamford-
Stevens reaction of the appropriate acetal to~ylhydrazone.~?~ The known con-
version of endo-(183; X = OAc) into endo-(184; X = 0; Y = H,OAc) is the
1
X Y
(183) (1 84) (185)
basis of a synthesis of (184; X = 0, Y = CH2).604Compound (186) has been
converted into teresantalic acid (187) (Scheme 5).605A straightforward synthesis
(1 86) (187)
Reagents: i, hv, acetone, 25 "C, 10 h; ii, NaH-HC0,Et-Et,O-EtOH, 25 "C, 4 2 h; iii, tosyl azide-
Et,N-CH,Cl,, 25 "C, 78 h; iv, hv, NaHC0,-THF-H,O, 25 "C, 45 min; v, LiNPr: (2.5
equiv.), THF, 50 "C, 1 h; vi, Bu"Li (1 equiv.), 50 "C, 1 h; vii, MeI, 25 "C, 16 h
Scheme 5
of camphenilanic acid [endo-(183; X = CO,H)], via (183; X = Br) and endo-

(183; X = CN), has been carried out from isocamphenilanic acid [exo-(183;
X = C02H)],606an optical resolution of which has been r e p ~ r t e d ; ~reaction
~~'~~"
of exo -( 183 ; X = C0,H) with 1,l'-carbonyldi-imidazole and LiAlH4 reduction
provides access to exo-( 183; X = CH0).606Further synthetic work concerns
ketopinoyl peroxides,6084-methylisocamphenilanic acid,609and attempts by
'02 J. M. Conia and G . L. Lange, J. Org. Chem., 1978,43, 564.

'
0
3 L. Borowiecki and M. Welniak, Roczniki Chem., 1977,51, 1751.
'04 N. H. Werstiuk and R. Taillefer, Canad.J. Chem., 1978, 56, 1134.
605 S. A. Monti and S. D. Larsen, J. Org. Chem., 1978, 43, 2282.
'06 G. Buchbauer, Monatsh., 1978,109, 3.
607 G. W. Hana and H. Koch, Arch. Pharm., 1978,311,498.
'08 Yu.A. Ol'dekop, N. A. Maier, A. A. Erdman,T. A. Rubakha, and I. A. Shingel, Vestsi Akad. Navuk
belarusk. S.S.R., Ser. khim. Navuk, 1978, ( l ) , 118.
'09 G. Buchbauer and I. Schrnidmayer, Monatsh., 1978,109,751.
-
de Mayo and colleagues to synthesize 4-methylcamphordithioquinone (it is
formed at 77 K but dimerizes on
Kreiser and colleagues have reinvestigated the structure of albene (Vol. 3, p.
58; Vol. 5 , p. 34; there is a discrepancy between the formulae used) and
established the structure as (188) by 13C n.m.r. analysis,611aby X-ray structure
determination of the isoalbene (189; X = H)derivative (189; X = SCH2Ph),611b
and by the synthesis of (-)-albene (188)from (+)-camphenilone [(184; X = H,H;
Y = O ) - e n a n t i ~ m e r ] ~and
" ~ of (*)-isoalbene (189; X = H) uia Diels-Alder reac-
tion and conversion into (189; X = SCH2Ph).611c It seems reasonable that albene
is a trisnorsesquiterpenoid.
Microbial oxidation of (+)-bornyl acetate (to 5-exo- and 5-endo-hydroxy-

borneol) using Helminthosporium satiuurn is more efficient and regiospecific than
that reported previously (Vol. 8, p. 51) with the enantiomer, in contrast to the
conversion of (+)- and (-)-bornyl acetate, using Fusarium culrnorurn, into
5 - exo - hydrox yborny 1 acetate .6 *
The full paper on the rearrangement of cations derived from 2-endo-aryl-
borneol in FS03H-S02C1F identifies additional cations (cf. Vol. 6, p. 37) and also
confirms the SOC1,-pyridine-catalysed syn-dehydration of 2-endo-phenyl-
~ ~ ~ crystallographic data for (-)-camphene-8-carboxylic acid
b o r n e 0 1 . ~X-Ray
(184; X = H,H; Y = E - C H C 0 2 H ) have been interpreted as supporting the
exo-methyl migration in the Nametkin rearrangement of camphene (184; X =
H,H; Y = CH2).79The steric and inductive effects of substituent groups at C-4613a
and other on the rates of base-catalysed exo- and endo-deuterium
exchange in various bicyclo[2,2,l]heptan-2-ones have been examined.
Photolysis of the spiro 2-oxo-2,5-dihydro-l,3,4-oxadiazolene derivatives
prepared from (+)-camphor semicarbazone proceeds in cyclohexene by C0,-
extrusion to yield the cyclohex-2-enylhydrazone (44%) and, through cyclo-
dimerization, the symmetrical camphor azine (53%) with only 3% of camphor
arising via the alternative CO/N2 extrusion pathway.614Pb(OAc), oxidation of
610 N. Jacobsen, P. de Mayo, and A. C. Weedon, Nouveau J. Chim., 1978,2,331.
611 ( a ) W. Kreiser, L. Janitschke, and L. Ernst, Tetrahed!on, 1978, 34, 131; (6) W. Kreiser, L.
Janitschke, and W. S . Sheldrick, J.C.S. Chem. Comm., 1977, 269; ( c )W. Kreiser and L. Janitschke,
Tetrahedron Letters, 1978,601. Full syntheticdetails for (-)-albene (188) have appeared recently, W.
Kreiser and L. Janitschke, Chem. Ber., 1979, 112, 408, and for (+)-isoalbene (189; X = H ) ; see
W. Kreiser, L. Janitschke, W. Voss, L. Ernst, and W. S . Sheldrick, Chem. Ber., 1979, 112,397. An
unusual feature of (188) synthesis is an endo-Nametkin rearrangement; for example, cf. ref. 79 and
Vol. 5, p. 31.
'I2 M. S . Allen, N. Darby, P. Salisbury, and T. Money, Tetrahedron Letters, 1978, 2255.
(a)F. C. Brown, E. Casadevall, P. Metzger, and D. G. Morris, J. Chem. Res. ( S ) , 1977,335; ( b ) N. H.
Werstiuk, R. Taillefer, and S . Banerjee, Canad. J. Chem., 1978, 56, 1140, 1148.
614 D. Daniil and H. Meier, Tetrahedron Letters, 1977, 3155.
Monoterpenoids 67
the 2-aminoindazole (20; x = 1, Y = NH2) to the corresponding 1,2,3-benzo-

triazine and photolysis yields (24; X = CN, Y = e t h ~ n y l ) . ~
Photolysis
~’ of the
cyclic N-ethyl-(+)-camphoric imide produces predominantiy the two expected
ring-expanded Norrish Type I1 bridged bicyclic keto-lactams together with some
(190; X = CONHCHO) which may result from Norrish Type I cleavage.616The
photochemical cleavage of homocamphor via an aldehyde or a keten pathway is
solvent-dependent ; it is known that in Et20-cyclohexylamine only the amide
results, whereas in THF-H20 the aldehyde (190; X = CH2CH2CHO)pathway
predominates over the keten pathway by 30 : l.617
Oxidation of the known lactone (191; X=H,H) with Cr03 yields (191;
X = 0),618 Chromyl acetate oxidations of exo- and endo-fenchyl acetates and of
(190) (191)
fenchone have been investigated; fenchone is oxidized primarily to the 6-keto-
derivative but the fenchyl acetates suffer oxidation at C-5 (keto- and exo-acetoxy-
products) in addition to oxidative conversion into diaceto~y-ketones.~’~ The
manganese(II1) acetate oxidation of camphene has been reinvestigated more
thoroughly (Vol. 6, p. 38) and extended to bornene which yields the lactones
(192)-(194) and the C-2-epimer of (194); (194) is the major product from
v (192)
0
(193) (194)
camphene oxidation.620Additional oxidation papers concern ozonolysis of
camphene (cleavage and Baeyer-Villiger products),621 peracid oxidation of
camphorimines (to chiral oxaziridines),1327133 anodic Oxidation of isoborneol to
(195),622mercuration of bornene with Hg0-HC104-NaC1 [to give (196) in
’ ~ oxymercuration-bromination of
addition to non-rearranged a d d u c t ~ ] , ~and
tricyclene to 2-bromotri~yclene.~~~
‘I5 I. Ito, N. Oda, S.-I. Nagai, and Y. Kudo, Heterocycles, 1977,8, 319.
‘I6 Y. Kanaoka, H. Okajima, and Y. Hatanaka, Heterocycles, 1977, 8, 339.
‘I7 S. C. Critch and A . G. Fallis, Canad. J. Chem.. 1977, 55, 2845.
Y. Hirose, M. Kuroiwa, M. Shibata, and A . Fujita, Chem. and Pharm. Bull. (Japan),1978,26,1003.
‘I9 J. Enqvist, Ann. Acad. Sci. Fennicae, Ser. A2, 1977,183, 1.
620 K. Witkiewcz and Z. Chabudzinsky, Roczniki Chem., 1977,51,2155; for earlier papers in thisseries,
see Vol. 8, pp. 43, 54, 57.
621 J. Tanaka, K. Takabe, M. Kawakita, M. Ito, and T. Katagiri, Nippon Kagaku Kaishi, 1978, 284.
‘’* P. S. Scholl, S. E. Lentsch, T. P. Steckel, and M. R. Van D e Mark, 170th A.C.S. Meeting, Chicago,
August 1975, Abstracts ORGN, No. 73. This paper was inadvertently omitted from earlier Reports.
‘23 E. V. Skorobogatova, L. N. Povelikina, and V. R. Kartashov, Zhur. org. Khim., 1978,14,663.
624 S . N. Suryawanshi and U. R. Nayak, Tetrahedron Letters, 1978,465; for related work, see ref. 640.
(195) (196)
Rassat has summarized some of his results on the stereochemistry of dissolving-
metal reduction of bicyclo[2,2,l]heptanones (cf.Vol. 2, p. 45).625Camphor is one
of a number of ketones investigated in mechanistic studies of sodium borohydride
reduction,626 lithium aluminium hydride and lithium alkoxyaluminium hydride
and tri-isobutylaluminium-amine complex reductions;628
camphoric anhydride reduction with lithium aluminium hydride is included in a
regioselectivity study of anhydride reduction.629The aluminium isopropoxide
reduction of 10-halogeno-camphor results in (190; X = CH,CHO) via the endo-
10-bromoborneol but not via 10-chloroborneo1.630
The conjugate bases of camphoroxime and 2-nitrobornane undergo elec-
trophile addition from the exo providing access to 2-exo-bromo-2-endo-
~ ~ 2-endo -nitrobornane; nitration of camphoroxime to the
n i t r ~ b o r n a n eand
nitrimine and 2,2-dinitrobornane, is also reported but attempts to obtain
2-exo-nitrobornane were L ~ ~ s u c c ~ s Dehydrohalogenation
s~u~.~~~ of 2-exo-
bromo-2-endo-nitrobornane (cf. Vol. 5 , p. 32, ref. 225) using AgSbF6 occurs
selectively to 4-nitrocamphene in CH2C12 but yields 1-nitrocamphene :4-
nitrocamphene/7 : 3 in Dehalogenation of 3-exo- bromocamphor
with AgSbF6-CH2C12 yields a mixture of lactones (presumably formed from
1,2,2-trimethylcyclohex-3-enylcarboxylicacid) in contrast to reaction with
3-endo-bromocamphor which yields 6-isopropenyl-6-methylcyclohex-2-enone
analogously to rearrangement of 3-diazocamphor with HSbF6 in CH2C12
(presumably via exo -protonation), although tricyclocamphanone is formed with a
catalytic amount of HSbF6.633The chemistry of o -nitrosocamphene (184; X =
H,H; Y = CHNO), which has pronounced 1,4-dipolar character, has been
investigated further (cf. Vol. 5, p. 32). Chromous chloride reduction of w -
nitrocamphene (184; X = H,H; Y = CHNO,) yields (197) presumably via (184;
X = H,H; Y = CHNO); reaction of w-nitrocamphene (184; X = H,H; Y =
C H N 0 2 )with fuming HBr followed by base yields the stable bridgehead nitrile
oxide (198)which reacts with methanolic KOH to yield (199) via the presumed
corresponding a,P -unsaturated n i t r o ~ o - d e r i v a t i v eThermal
. ~ ~ ~ decomposition of
the monoanion of the (2,4,6-tri-isopropylbenzene)sulphonylhydrazoneof
camphor (to tricyclene via the carbene) occurs under milder conditions than with
625 A. Rassat, Pure Appl. Chem., 1977,49,1049.
626 J.-C. Perlberger and P. Miiller, J. Amer. Chem. SOC.,1977,99,6316.
627 K.E.Wiegers and S. G. Smith, J. Org. Chem., 1978,43,1126
628 T.Suzuki, M. Itoh, S. Ogawa, and Y . Takegami, Bull. Chem. SOC.Japan, 1978,51, 2664.
629 M. M.Kayser and P. Morand, Canad. J. Chem., 1978,56,1524.
630 N.Proth, Rev. Tech. Luxemb., 1976,68.195 (Chem. Abs., 1977,87,135 965).
631 S. Ranganathan, H. Raman, and C. V. Srinivasan, Tetrahedron, 1978, 34, 3129.For reports of
2-endo-chloro-2-exo-nitrosobornane,74 see Vol. 6, p. 41,ref. 236.
632 J.-P. BeguC, C. Pardo, and J. Sansoulet, J. Chem. Res. ( S ) , 1978,52.
633 J.-P. BCguC, M. Charpentier-Morize, C. Pardo, and P. Sansoulet, Tetrahedron, 1978,34,293.
634 S.Ranganathan, B. B. Singh, and C. S. Panda, Tetrahedron, 1977,33,2415.
Monoterpenoids 69
the camphort~sylhydrazone,~~~ the 3-em -deuterio analogue of which may be

cleaved most effectively to the ketone, without enolization, using N-bromosuc-
~inimide.~~~
Other papers of interest in this section report an improved camphor ring-
expansion via Lewis acid-catalysed benzyl diazoacetate addition,637further
details of camphor cleavage to (24; X = C 0 2 H , Y = CHC1,) using CC14-KOH-
B u ' O H ~and ~ ~ of thio-Claisen rearrangements of allylic enethiolic ethers of
t h i o ~ a m p h o rhypobromous
,~~~ acid cleavage of tricyclene [to (200; X = CHBr),
(200; X = OH,CH2Br), and (200, X = OH,Me)],640acetalization of 2-exo,3-exo-
X 34 Br
d i h y d r ~ x y b o r n a n e ,reaction
~~~ (with Wagner-Meerwein rearrangement) of
camphene with phenylselenenyl chloride,22s synthesis of aza-heterocyclic
camphor derivatives,642 manganese(II1) acetate oxidation of N-vinylcam-
p h ~ r i m i d e , and
~ ~ ~ the synthesis of nitrogen mustards from hydroxy-
methylenecamphor and related compounds.644
Bicycle[3,l,l]heptanes.-Semi-empirical C N D 0 / 2 calculations on pinocam-

phone [truns-(201; X = O)], isopinocanqhone [cis-(201; X = O)], verbanone
[truns-dihydro-(202; X = O)], and isoverbanone [cis-dihydro-(202; X = O)] are
consistent with preferred boat conformation^.^^^ In a discussion of alkylation and
635 A. R. Chamberlin and F. T. Bond, J. Org. Chem., 1978, 43, 154; for the related dianion
decomposition to vinyl-lithiums, see ref. 227.
636 P. K. Freeman and J. R. Balyeat, J. Org. Chem., 1977,42, 3205.
637 S. W. Baldwin and N. G. Landmesser, Synth. Comm., 1978, 8, 413; cf the poor results using a
palladium-catalysed ring-expansion sequence reported in Vol. 8, p. 52, ref. 467.
C. Y. Meyers and V. M. Kolb, J. Org. Chem., 1978, 43, 1985.
639 D. Barillier, L. Morin, D. Paquer, P. Rioult, M. Vazeux, and C. G. Andrieu, Bull. SOC.chim. France,
1977,688; see Vol. 7, p. 40 for the preliminary communication.
640 S. N. Suryawanshi and U. R. Nayak, Tetrahedron Letters, 1977,3595; for related work, see ref. 624.
641 A. Bazbouz, H. Christol, J. Coste, and F. PlCnat, Bull. Suc. chim. France, 1978, 305.
642 S. Seube, A.-M. Lamazoukre, and J. Sotiropoulos, J. Heterocyclic Chem., 1978, 15, 343.
643 K. Yanagi and T. Nishiyama, Nippon Kaguku Kuishi, 1978,404.
644 E. Mariani, A. Tasca, G. Bignardi, and P. Schenone, Farmuco, Ed. Sci.,1978, 33,612.
645 J. Fournier, J. Chem. Res. ( S ) , 1977,320;for earlier conformational papers, see Vol. 2, p. 49; Vol. 5,
p. 36; Vol. 6, p. 41.
Robinson ring annulation of nopinone, Thomas et al. have pointed out dis-
crepancies between two previous assignments (Vol. 6, p. 41, ref. 304 and Vol. 7,
p. 3, ref. 5) of the 13C n.m.r. for verbenone (202; X = 0),isoverbanone [cis-
dihydro-(202; X = O)], and cis- and trans-myrtanol [cis/trans-dihydro-(203;
X = CH,0H)].64h Electron-impact mass-spectral fragmentation of epoxychry-
santhenone (204) may occur by loss of CO, from a molecular ion via a lactone-
type intermediate reminiscent of the known (Vol. 5, p. 27) photorearrangement
product, filifolide A (205), although electron-impact rearrangement of (204) to
(205) does not occur.647
(201) (202) (203) (204) (205)

Myrtenol (203; X = CH,OH) may be obtained most efficiently from the more
stable secondary allylic alcohol (+)-trans-pinocarveol (30; enantiomer) via
bromination with PBr3 to the rearranged bromide (203; X = CH,Br) [(30) :(203;
X = CH,OH)/85 : 151; ester thermolysis and isomerization-oxidation were less
effective; and the direct acid-catalysed isomerization was not
Intramolecular cyclization of (206), which is readily synthesized via
trifluoroacetic anhydride cyclization of 4-methylcyclohex-3-enylacetic acid to
(186), affords (207) which is cleaved to (208; X = NH,) in a synthesis of (&)-a-
(206) (207) (208)

~ i n e n e . ~(-)-p
~ ' -Pinene is isomerized rapidly to (-)-a-pinene using potassium
3-aminopropylamide in 3-aminopropylamine, with essentially quantitative iso-
meric and optical conversion.65o The ~ y n t h e s i s 'of ~ ~ monoisopinocampheyl-
borane (-100% optical purity) from (+)-a-pinene of lower optical purity143gand
its conversion into (-)-isopinocampheol [(2R73R)-(201; X = H,OH)] of very
high optical purity ([a]h5= -35.79'; benzene) has been The
Organic Syntheses preparation of (+)-isopinocampheol from (-)-a -pinene of
similar optical purity (Vol. 4, p. 56, ref. 267) gives a sample with [a]g= +32.8"in
benzene. s -Trioxan and N-methylanilinium trifluoroacetate effects direct a -
methylenation of nopinone in high yield.651
646 Y. Bessiere, M. Bartheltmy, A. F. Thomas, W. Pickenhagen, and C. Starkemann, Nouveau J. Chim.,
1978, 2, 365.
647
S. Eguchi, Y. Uchio, A. Matsuo, M. Nakayama, and S. Hayashi, Chem. Letters, 1978, 1029.
648 Y. Bessitre, E. Reca, F. Chatzopoulos-Ouar, and G. Boussac, J. Chem. Res. (S), 1977, 302; for
related work in the p-menthane series, see ref. 515.
649 S. D. Larsen and S. A. Monti, J. Amer. Chem. SOC.,1977,99,8015.
C. A. Brown, Synthesis, 1978, 754.
J.-L. Gras, Tetrahedron Letters, 1978, 2111.
Monoterpenoids 71
a -Pinene is metabolized by Pseudurnonas putida to acyclic unsaturated C,,

acids in addition to degraded and of the four verbenols only (+)-trans-
verbenol [trans-(202;X = H,OH)] is oxidized [to (+)-verbenone (202; X = O)]
using cell-free callus from Cannabis ~ a t i v a . ~ ~ ~
The structure of the major FeC1,-catalysed ene adduct of chloral to (1S,5S)-
(-)-P-pinene (Vol. 8, p. 54)is (209).96Preferred ene reaction of PhS0,NSO with
P-pinene has been used for the almost quantitative separation of a- and
; ~ ~ ~ application of this reaction allows the conversion of a -
P - ~ i n e n e another
pinene into P -pinene via a triple allylic transposition sequence of ene-reaction,
reduction, reductive silylation, and hydroly~is.'~~ Ene reactions of p -pinene
under pressure have been observed (74-100% yields) at room temperature thus
~ ~ ~ full papers on a -
limiting, for example, retro-ene s i d e - r e a c t i o n ~ .The
pinene/allo-ocimene pyrolysis (cf. Vol. 7, p. 12)654and on the thermal rear-
rangement of (208; X = H or Me) have been published (Vol. 4, pp. 61, 62);655
(208; X = H ) is to yield only (210) in contrast to unpublished
observations of Frater who has reported the rearrangement of (210) to (208;
X = H ) and the formation of p-menthadiene derivatives from (208; X = H or
0 - 1 . ~ ~ ~
(209) (210)
The rearrangement of (+)-2a,3cr!-epoxypinane on alumina depends upon how
the alumina is modified; on A1,03-NaOH, the major product is (-)-trans-
pinocarveol (30; 93%) but on Al2O3-LiC1pinocamphone [trans-(201; X = O)]
predominates. lg7 Rearrangement of the two 2,l O-epoxypinanes over A1203-
NaOH gives closely similar mixtures of trans-myrtanal, myrtenaI (203;X = CHO,
enantiomer), (-)-trans-myrtanol, and (-)-myrtenol (203; X = CH,OH, enan-
tiomer), although there is an inconsistency over the formula and the sign of the
optical rotation used for (--)-myrten01~~~
(for example, see that used by Klein and
Rojahn22). Hydroboration-oxidation of (+)-2a,3a-epoxypinan-4-one yields
(2R)-(211):(2S)-(211)/70:30 via (212) with no effect of added LiBHq.657
652 N. J. Tudroszen, D. P. Kelly, and N.F. Millis, Biochem. J., 1977, 168, 315.
653 J. A . Gladysz and Y. S. Yu, J.C.S. Chem. Comm., 1978, 599.
654 K. J. Crowley and S. G . Traynor, Tetrahedron, 1978, 34,2783.
655 Y. Bessiere, C. Grison, and G . Boussac, Tetrahedron, 1978, 34, 1957.
656
G . Frater, 2nd International I.U.P.A.C. Symposium on Organic Synthesis, Jerusalem-Haifa,
September 1978; personal communication.
657 A . Uzarewicz and E. Segiet-Kujawa, Polish J. Chem., 1978, 52, 6 3 .
Hydroboration of (+)-verbenone (202; X = 0) and treatment with hydroxyl-

amine-0-sulphonic acid results in a 65% yield of (+)-cis-8-pinene (213)658by
elimination, with no resultant a r n i ~ ~ eDehydrated
.~~’ neutral alumina may be used
for the room-temperature concerted 172-eliminationfrom 10-pinanyl tosylate to
yield 0-pinene (70%) and some a-pinene (14%) with little rearrangement to
camphene.660The addition of diethyl NJV-dichlorophosphoroamidate to (-)-a-
pinene yields (+)-(214)661and the structure of the adduct (-)-(13) from MePC12-
AlCl, addition to (-)-a-pinene has been confirmed by X-ray anal~sis.~’ The
addition of HCNO to a- and P-pinene was reported earlier.535
(213) (214)
Further papers in this section include additional reports of the thermal rear-
rangement of a-pinene662aand P-pinene,662b another report of salicylic acid-
catalysed rearrangement of a- and P-pinene (see Vol. 3, p. 71),663epoxidation of
a -pinene in the presence of molybdenyl a c e t y l a ~ e t o n a t e ,oxidation
~~~ of a -
pinene in the presence of polychelates of bis(aminopheno1s) and C O I ~ ,another ~~’
report of anodic oxidation of a- and p-pinene,666the full paper on B2H6-LiBH4
reduction of (+)-2a, l O - e p ~ x y p i n a n efurther
, ~ ~ ~ details of chrysanthenone reduc-
tion (cf. Vol. 7, p. 43)668and of the conformations of lactams and derivatives
obtained from Beckmann rearrangement of isopinocamphone oxime [cis-(201;
X = NOH)] (cf.Vol. 6, p. 43),669the nitration of (-)-isopinocamphone [cis-(201;
X = 0),enantiomer] with cerium(1v) ammonium nitrate [to yield (+)-2-nitro-
pinocamphone together with fragmentation and rearrangement the
658 A. Uzarewicz, E. Segiet-Kujawa, and I. Uzarewicz, Roczniki Chem., 1977, 51, 1537. Fluoroboric
acid gives the same result. The cis- and trans-8-pinenes have not been named fully by Klein and
Roj ahn .22
659
For the preparation of isopinocampheylamine by this method, see M. W. Rathke and A. Millard,
Org. Synth., 1977,57, no. 2049 accepted for testing.
660
G. H. Posner, G. M. Gurria, and K. A. Babiak, J. Org. Chem., 1977,42,3173.
66 1
B. Olejniczak, K. Osowska, and A. Zwierzak, Tetrahedron, 1978, 34, 2051. A violent explosion
during the preparation of this reagent has been reported recently; B. J. Walker, Chem. in Britain,
1979,15,65.
662
J. de Pascual Teresa, I. Sanchez Bellido, M. R. Alberdi Albistegui, A. San Feliciano, and M. Grande
Benito, ( a ) Anales de Quim., 1978,74, 301; ( 6 ) ibid., p. 305.
663
I. I. Bardyshev, E. N. Manukov, and V. A. Chuiko, Vestsi A k a d . Navuk belarusk. S.S.R., Ser. khim.
Nauuk, 1977, (6), 87.
664
A. M. Romanikhin, Izvest. Vyssh. Uchebn. Zaved., Khim. khim. Tekhnol., 1977, 20, 1807.
665
T. K. Popova and N. I. Popova, Izvest. Vyssh. Uchebn. Zaved., Khim. khim. Tekhnol., 1977, 20,
821.
666
M. Kasano, Y. Sakai, K. Yokoi, Y. Matsubara, and C. Yoshimura, Kinki Daigaku Rikogakubu
Kenkyu Hokoku, 1977, (12), 93 (Chem. A h . , 1977,87, 184 699). See Vol. 4, p. 57 for the earlier
report. Anodic oxidation of limonene is also discussed.
667
A. Uzarewicz and E. Segiet-Kujawa, Roczniki Chem., 1977, 51, 2147. Repetition of most of the
previously reported (Vol. 6, p: 43) (and uncited) paper does not seem justified to this Reporter.
668
C. A. N. Catalan, D. J. Merep, and J. A. Retamar, Rivista Ital. Essenze-Profumi, Piante Ofic.,
Aromi, Saponi, Cosmet., Aerosol., 1977,59,480.
669
C. Wawrzenczyk and A. Zabza, Bull. Acad. polon. Sci., Skr. Sci. chim., 1977, 25, 605.
670
J. de Pascual Teresa, I. Sanchez Bellido, B. Corrales, and M. Grande Benito, Anales de Quim., 1977,
73, 1377.
Monoterpenoids 73
aminomethylation of verbenone (202; X = 0),671 and Wagner-Meerwein rear-

rangements on adding phenylselenenyl chloride to Q - ~ i n e n e . ~ ~ ~
Bicyclo[4,l,0]heptanes.-3-Methoxy-4-iodocarane has been reported to

explode violently on standing.672
13
C N.m.r. chemical shifts of a number of monoterpenoids of this class are
included in a study of bicycl0[4,l,O]heptanes.~~~ A further paper in a series on
enthalpies of combustion and formation concerns the 3 , 4 - e p o ~ y c a r a n e s . ~ ~ ~
(+)-Car-2-ene and (-)-car-2-ene of high optical purity have been synthesized
from the respective (-)- and (+)-trans-caran-2-onesYvia the analogous and
uncited tosylhydrazone/methyl-lithium route used by Cocker et al. for synthesiz-
ing (-)-cis-car-4-ene (Vol. 1, p, 47), thus providing access (Vol. 2, p. 29, ref. 108)
from the readily available (+)- and (-)-dihydrocar~ones.~~’ Cocker et al. have
synthesized norcaran-3-one (via dibromocarbene addition to 4,4-dimethoxy-
cyclohexene and treatment with lithium dimethylcuprate) from which car-2-ene,
car-3-eneYand car-3(10)-ene were prepared.676
In the carane series, the known dependence of epoxy-ring opening on steric
factor^^^^^'^ and of the cyclopropane ring on electronic has been
examined further using (215; X = H,H; Y = 0 ) ;(215; X = 0, Y = H,H), (215;
X = H , H ; Y=H,OH), and (215; X=H,P-OH; Y=H,H). The direction of
cyclopropane ring opening in ethereal HCl is governed by the
influence of the carbonyl group but does not occur in the alcohol series; the
electronic influence of an adjacent carbonyl group partly overcomes steric
inhibition of nucleophilic attack in epoxide ring opening [e.g. (216) : (217)/7 : 1is
obtained from (215; X = O , Y=H,H), cf. ref. 6 7 7 ~ 1whereas an adjacent
hydroxy-group stereospecifically directs epoxide ring opening distant from it even
when opposed by steric hindrance to nucleophilic attack [e.g. (218) is obtained
from (215; X = H,H; Y = H , c x - O H ) ] . B2H6-LiBH4
~~~ hydroboration of (+)-
3a,4a -epoxycarane yields (-)-(219) with minor amounts of (3R)-(+)-(220) or
the diols (22 1) depending upon the mode of addition; (-)-3P,4p epoxycarane
yields (222; 93%) and (3S)-(-)-(220) with no effect of the order of reagent
addition.679A fourth paperlg7in a series discussing oxiran rearrangements over
silica gel and alumina reports a decided preference for trans- A3,’o-caren-4-01
formation (63%) from (+)-3aY4a- epoxycarane over sodium hydroxide-modified
671 H. Krieger, A. Kojo, and A. Oikarinen, Finn. Chem. Letters, 1978, 185.
672 D. R. Dimmel, Chem. Eng. News, 1977,55(27), 38.
673 T. 1. Pekhk, K. E. Kooskora, E. T. Lippmaa, V. I. Lisenkov, G. V. Deshchits, and I. I. Bardyshev,
Vestsi Akad. Navuk belarusk. S.S.R., Ser. khim. Navuk. 1977, (l),96.
674 M. P. Kozina, V. A. Aleshina, G. L. Gal’chenko, G. V. Deshchits, and I. I. Bardyshev, Vestsi Akad.
Navuk belarusk. S.S.R., Ser. khim. Navuk, 1977, (6), 94. For earlier papers, see Vol. 6, p. 45 and Vol.
7, p. 44.
675 P. Brunetti, F. Fringuelli, and A. Taticchi, Gazzetta, 1977, 107, 433.
676 W. Cocker, N. W. A. Geraghty, and D. H. Grayson, J.C.S. Perkin I, 1978, 1370.
677 ( a ) E.g. for acid-catalysed cleavage, see Vol. 4, p. 64, ref. 305 and Vol. 7, p. 45, ref. 439a; ( 6 ) for
LiAlH4 cleavage, see Vol. 7, p. 45, ref. 4396 and Vol. 8, p. 57, ref. 519; (c) e.g. see Vol. 2, p. 56, ref.
233. In Vol. 4, p. 64 the reference number on lines 3 and 5 should be 306 and not 305.
678 B. A. Arbuzov, Z. G. Isaeva, and A. N. Karaseva, Proc. Acad. Sci. (U.S.S.R.), 1977, 237, 626.
679 A. Uzarewicz, E. Zientek, and I. Uzarewicz, Polish J. Chem., 1978,52,389; cfi Vol. 8, p. 57. This
paper, and earlier papers in the series, would be clearer with better formulae drawing and more use of
formulae numbers in the text; in addition, the international numbering system of the caranes is not
used.
(219) (220) (221) (222)

alumina compared with alumina alone; alumina modification with sodium
chloride gives results similar to those with silica gel (see references therein for the
earlier work). 197 Another paper680a from Cocker's laboratory reports a re-
examination of an earlier report6'Ob of treating (+)-carane-3&4a -diol with
sulphuric acid; the major products are (223)-(226).680"
(223) (224) (225) (226)

Further papers in this section include a straightforward synthesis of 4-methyl-
car-3-ene and some derivatives,681another report of cobalt-catalysed air oxida-
tion of car-3-ene (cf. Vol. 7, p. 45),682 anodic oxidation of car-3-ene to yield
2,6,6-trimethylcyclohepta-2,4-dienol predominantly (together with some p -
menthane a further paper (cf.Vol. 8, p. 57) on dehydrogenation of
car-3-ene over chromia and chromia-alumina the full paper on
isomerization of 2,3- and 3,4-epoxycaranes over solid acids and bases,685
dimerization of (-)-cis-caran-4-one to 4-caranylidenecarane (mostly trunsoid)
using the diamagnetic complex [THF,C12MgzTi]z,686(+)-car-3-ene nitroso-
680 ( a ) W. Cocker and D. H. Grayson, J.C.S. Perkin I, 1978, 155; ( 6 ) P. P. Pillay and J. L. Simonsen,
J. Chem. SOC.,1928, 359.
"' L. K. Novikova, 0. B. Skripnik, G. Sh. Bikbulatova, S. G. Vul'fson, 2. G . Isaeva, and A . N.
Vereshchagin, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1978, 605.
682 H. Sadowska, J. Kulesza, and J. Podlejski, Tlustcze, Srodki Piorace, Kosmet., 1976,21,393 (Chem.
Abs., 1978, 88, 23 163); for an earlier report, see Vol. 7, p. 45.
683 M. Kasano, K. Matsumoto, F. Hosogi, Y . Matsubara, and C. Yoshimura, Kinki Daigaicu Riko-
gakubu Kenkyu Hokoku, 1977, (12), 89; Chem. Abs., 1977,87,184 698 names this product poorly.
684 V. Krishnasamy, Canad. J. Chem., 1978, 56, 1994.
K. Arata, J. 0. Bledsoe, jun., and K. Tanabe, J. Org. Chem., 1978, 43, 1660; for the (unac-
knowledged) communication, see Vol. 8, p. 57.
P. Sobota, C. Wawrzenczyk, and J. Utko, Bull. Acad. polon. Sci., Se'r. Sci. chim., 1977, 25, 957.
Monoterpenoids 75
and the rapid dealkylation of B-(4- isocaranyl)-9-borabicy-

clo[3,3,l]nonane with benzaldehyde.688
9 Furanoid and Pyranoid Monoterpenoids

The occurrence and syntheses of rose oxides, dihydrorose oxides, rosefuran, and
nerol oxides, together with related compounds, have been reviewed.689The
structure of a cyclic monoterpenoid ether from Artemisia tridentata, which is
related to the santolinyl monoterpenoids, has been confirmed (cf.Vol. 7, p. 20) as
(227) and renamed artemiseole (cf. Vol. 8, p. 58 for an incorrect structural
dedu~tion).~~' Interestingly, another new component of A. tridentata, the (3s)-
diastereoisomer of (74), with formic acid yields (227) in contrast to (74) which
yields the acyclic aldehyde (228).690It is possible that some of the 31% of
unidentified components in the essential oil of A . annua may correspond to these
new The quinone (229) has been isolated from Lithospermum
e~ythrol'hizon,~~~and further details on the presence of aeginetolide in Aeginetia
indica have been
I
(227) (228) (229)

The full paper (Vol. 8, p. 58) on the biogenetic-type synthesis of the linalyl
oxides has been published383and dihydro-ocimenoyl oxide (230) has been
synthesized by the regiospecific reaction of 2-methylbutanal with the y-carbon
atom of a,a-dimethylallyltrimethylsilanecatalysed by TiC14, presumably via
cyclization of the corresponding y - ~ h l o r o - a l ~ o h oStraightforward
l.~~~ syntheses
of perillene (231; X = H,H) and egomaketone (231; X = 0)involve prenylation
X
(230) (231)
'"C. P. Mathew and J. Verghese, Indian J. Chem., 1977, lSB, 1081.
M. M. Midland, A. Tramontano, and S. A. Zderic, J. Organometallic Chem., 1978,156,203; cf. Vol.
8, p. 6.
'89 Y .R. Naves, Rivista Ital. Essenz-Profumi, Piante Ofic., Aromi, Saponi, Cosmet., Aerosol., 1978,60,
265.
690 T. A. Noble and W. W. Epstein, Tetrahedron Letters, 1977, 3931; see also ref. 406.
691 E. V. Georgiev, N. S. Genov, R. D. Lazarova, and G. P. Gantchev, Rivista Ital. Essenre-Profumi,
Piante Ofic., Aromi, Saponi, Cosmet., Aerosol., 1978, 60, 302.
692 0. E. Krivoshchekova, S. A. Fedoreev, V. A. Denisenko, and 0. B. Maksimov, Chem. Natural
Compounds, 1977,13,586.
693 S . S . Dighe, S. V. Manerikar, and A. B. Kulkarni, Indian J. Chem., 1977, lSB, 546; see Vol. 6, p. 47
for the earlier report.
of 2-(3'-furyl)-1,3-dithianfollowed by appropriate d e ~ u l p h u r a t i o nIrradiation

.~~~
of furan and 4-methylpentanal in the presence of methanesulphonic acid gives,
after oxidation, a low yield (12%) of perillaketone [dihydro-(231; X = O)],""" the
corresponding heterocyclic sulphur analogue of which is available from the
efficient Pd(OA~)~-catalysed reaction of 3-bromothiophen with 4-methylpent-l-
en-3-01.~" Prenylation of the lithio-enolate of 2-methylbut-2-enolide gives 40%
of the y-prenylbutenolide which is readily reduced to rosefuran (232),696which is
also reported to be obtained by Cu-Mg coupling of 2-bromo-3-methylfuran and
prenyl The cis- and trans-rose oxides (233) have been prepared with
little novelty via 5-hydroxycitronellol,6g*and more usefully (36% yield) by the
one-step reaction of citronellol with N-iodosuccinimide in CC14.699 A stereocon-
trolled synthesis of (-)-cis-rose oxide [cis-(233)] from D-glucose via the Cerny
1
(232) (233)
epoxide (234) is shown in Scheme 6.'" Another synthesis of the rose oxides (233)
aooo0 0
is based upon routine modifications of (235) which results from reaction of
CH,OAc CH ,OTr
i, 4 iii-vii ~
OAc
0 OH OAc OMS
(234)
1
ocHo
viii
0 cis-(233) 2
1
e --
ix-xi
C H ,OTr
Me'
Reagents: i, LiCuMez; ii, BF,,Et*O-Ac20; iii, Bu3SnSEt-SnC14; iv, NaOMe-MeOH; v, Raney
Ni(W-4)-EtOH-NaBH4; vi, TrC1-py; vii, MsC1-py; viii, NaI-HMPA, 100 "C; ix, H2-
Pd/C; x, Arnberlist 15-MeOH; xi, pyridinium chlorochromate; xii, Me2C=PPh3
Scheme 6
694 T. Kitamura, Y. Kawakami, T. Imagawa, and M. Kawanisi, Synth. Comm., 1977,7,521.

695 Y. Tarnaru, Y. Yamada, and Z.-I. Yoshida, Tetrahedron Letters, 1977, 3365.
b96 D. R. Gedge and G. Pattenden, Tetrahedron Letters, 1977, 4443.
697 A. Takeda and K. Nihama, Jap. P. 136 162/1977 (Chem. A h . , 1978,88,170 342). This synthesis is
conceptually the same as that reported previously by A. Takeda et al. (Vol. 8, p. 59).
698 J. S. Patel, H. H. Mathur, and S. C. Bhattacharyya, Indian J. Chem., 1978, 16B,188; for related
work, see Vol. 1, p. 48; Vol. 3, p. 84; Vol. 7, p. 46.
699 S. C. Taneja, K. L. Dhar, and C. K. Atal, J. Org. Chem., 1978,43,997.
700 T. Ogawa, N. Takasaka, and M. Matsui, Carbohydrate Res., 1978,60, C4.
Monoterpenoids 77
(235)
formaldehyde with the telomer 2,6-dimethylo~ta-1,3,6-triene.~~~ The con-
formations of the rose oxides (233) and related compounds have been investi-
gated by 13Cn.m.r.702The course of dehalogenation of 1,3-dibromo-3-methyl-
butan-2-one in the presence of isoprene is modified further (cf.p.62 and Vol. 8, p.
48) by using Cu-NaI, when cyclohept-4-enone and vinylcyclopentanone forma-
tion is suppressed in favour of (236) and the minor product (237), both of which
may undergo [3,3] sigmatropic rearrangement to cyclohept-4-enones7 e.g. (237)
to karahanaenone (27; X = O).5716 In a study of brominative (Br,-AgBF,) and
acid-catalysed cyclization of homogeranic acid (cf. Vol. 4, p. 5 ) , it has been
established that the trans -1actones are kinetically favoured over the ther-
modynamically favoured ~ i s - l a c t o n e s LY; ~-phenylselenylation
~~ of the lactones
(238), oxidation, and thermal extrusion of benzenselenenic acid yields dihy-
droactinidiolide (239)703of which further details of related synthetic work have
been
10 Cannabinoids and other Phenolic Monoterpenoids

The structure of isoxanthochymol has been revised [to reposition a prenyl double
bond into a terminal position in keeping with the structure of xanthochymol
reported last year (Vol. 8, p. 60)]’”’ despite an earlier (incomplete) reportlo2of an
X-ray structure determination. Further details (cf. Vol. 7, pp. 48, 49) of the
chemistry and structures of (-)-bruceol (14; X = OH, Y = H),97 (*)-deoxy-
bruce01,~~ chromenes and citrans produced from phloroacetophenone and
phloroglucinaldehyde by citral c ~ n d e n s a t i o nand
, ~ ~ rubranine9’ have been pub-
lished; in a related paper the isolation of (-)-rubranhe from Aniba rosaeodora
701 T. Yamato and M. Nakamura, Rivistu Ital., Essenze-Profumi, Piante Ofic.,Aromi, Saponi, Cosmet.,
Aerosol., 1978, 60, 142 (VIIth International Congress of Essential Oils, Kyoto, October 7-11,
1977, Abstract No. 83).
702 E. Kleinpeter, Ch. Duschek, and M. Muhlstadt, J. prukt. Chem., 1978, 320, 303.
703 T. R. Hoye and M. J. Kurth, J. Org. Chem., 1978,43, 3693.
704 K. Uneyama, M. Kuyama, and S. Torii, Bull. Chem. SOC.Japan, 1978,51,2108; cf. Vol. 7, p. 47. For
related patents, see S. Torii, K. Uneyama, and M. Hisayama, Jap. P. 100 462/1977 (Chem. Abs.,
1978, 88;23 198); S. Torii, K. Uneyama, I. Kawahara, and K. Ito, Jap. P. 106 846/1977 (Chem.
A h . , 1978,88,89 888); K. Uneyama, G. Kuyama, and S. Torii, Jap. P. 106 859/1977 (Chem. Abs.,
1978, 88, 121 458).
S. C. Basa, P. Mahanty, and D. P. Das, Chem. and Ind., 1978, 166.
and a further examination of suggested biogenetic-type synthetic work (cf.Vol. 4,

p. 75) has been Alliodorin (as its dimethyl ether) has been
synthesized again .707
Tetrahydrocannabivarinic acid, cannabidivarinic acid, cannabichromevarinic
acid, and cannabigerovarinic acid are the C-3" carboxylic acid derivatives of
known propyl side-chain c a n n a b i n ~ i d sand
, ~ ~others
~ are propyl homologues of
cannabichromanone, cannabielsoin, and cannabielsoic acid B.709Turner et al.
have reported an additional triol (240) from Cannabis s ~ t i v u . ~ ' ~
Several X-ray structure determinations have been reported earlier. 103-106

Cannabinoid analytical papers concerning cannabin01,'ll A1-THC,712*713 7-
h y d r ~ x y - A ' - T H C , and
~ ~ ~A1-tetrahydrocannabinol-7-oic and a further
paper on the use of silyl ethers for g.c.-m.s. analysis of cannabinoid~~" have been
published. M.S. fragmentation patterns of a number of cannabinoids and their
pentyl side-chain homologues have been and metalloimmunoassay
of A6-tetrahydrocannabinol-7-oicacid has been
The synthons (241) condense718with olivetol, a useful synthesis of which has
been p ~ b l i s h e d , to
~'~ yield A'-THC derivatives which do not undergo conversion
into the A6-THC analogues in the presence of Two approaches to the
synthesis of side-chain-hydroxylated tetrahydrocannabinoids involve the well-
706
I. B. de Alleluia, R. B. Fo, 0. R. Gottlieb, E. G. Magalhaes, and R. Marques, Phytochemistry, 1978,
17, 517.
707
0. P. Vig, S. D. Sharma, N. K. Verma, and V. K. Handa, Indian J. Chem., 1977,15B, 988; cf.Vol. 7,
p. 48.
708
Y. Shoyama, H. Hirano, H. Makino, N. Umekita, and 1. Nishioka, Chem. and Pharm. Bull. (Japan),
1977,25,2306. The ~arboxy-'~C-labelledacids have also been synthesized; Y. Shoyama, H. Hirano,
and I. Nishioka, J. Labelled Compounds, 1978, 14, 835.
709
H. Grote and G. Spiteller, J. Chromatog., 1978, 154, 13.
710
A. Elsohly, E. G. Boeren, and C. E. Turner, Lloydia, 1977,40,619(Proceedings of the 18th Annual
Meeting of the American Society of Pharmacognosy; August 1977, Seattle, Washington). An
accompanying triol was reported last year (Vol. 8, p. 61).
7 1I
P. J. Twitchett, P. L. Williams, and A. C. Moffat, J. Chromafog., 1978,149, 683.
712
S . L. Kanter, L. E. Hollister, and K. 0.Loeffler, J. Chromatog., 1978,150,233; P. L. Williams, A. C.
Moffat, and L. J. King, ibid., 1978,155,273; D. Rosenthal, T. M. Harvey, J. T. Bursey, D. R. Brine,
and M. E. Wall, Biomed. Mass Spectrometry, 1978, 5 , 312; J. L. Valentine, P. J. Bryant, P. L.
Gutshall, 0. H. M. Gan, P. D. Lovegreen, E. D. Thompson, and H. C. Niu, J. Pharm. Sci., 1977,66,
1263.
713
J. Rosenfeld, Analyt. Letters, 1977, 10, 917.
714
S . L. Kanter and L. 8.Hollister, J. Chromatog., 1978, 151, 225.
715
D. J. Harvey, J. Chromatog., 1978,147, 291.
716
T. B. Vree, J. Pharm. Sci., 1977,66, 1444.
717
M. Cais, S. Dani, Y. Eden, 0. Gandolfi, M. Horn, E. E. Isaacs, Y. Josephy, Y. Saar, E. Slovin, and
L. Snarsky, Nature, 1977,270,534.
718
D. B. Uliss, G. R. Handrick, H. C. Dalzell, and R. K. Razdan, J. Amer. Chem. SOC.,1978,100,2929.
719
A. Focella, S. Teitel, and A. Brossi, J. Org. Chem., 1977, 42, 3456.
Monoterpenoids 79
known condensation of p-mentha-2,8-dien- 1-01with C-5 -substituted resorcinols

as the key step; one involves modifying an alkanoic ester ~ide-chain~~' and the
other the elaboration of a 4'-( 1,3-dithian-l-y1) group.721Conversion of A1-3,4-
cis -THC into A6-3,4-trans-THCusing BBr3involves predominant epimerization
at C-4.722Other papers of synthetic interest concern an improved synthesis of
(f)-~annabichrornene,~'~ 1-a~acannabinoid,~'~1-ketocannabin~id,''~ 4 -
hydroxy~oumarin,~~~ and 4-hydroxythio~oumarin~~~ analogues, and the synthesis
of A6-THC-C-4'-glucuronide727 which has also been isolated from mouse liver in
V ~ V O . ~ ~ ~
The formation of O-glucuronides has been observed during in vivo cannabinol
metabolism in the mouse and rat and compared with A'-THC and cannabidiol
m&abolism (cf. Vol. 7, p. 51; Vol. 8. p. 63);729additional anticipated in vivo
metabolites are reported in two further papers.73oAnother report of the micro-
biological oxidation of the pentyl side-chain of cannabinoids using Syncephalas -
trurn racernosurn (Vol. 7, p. 5 1) identifies 4",5"-bisnor-3"-hydroxycannabidiol
as a
major cannabidiol metabolite and includes data on Mycobacterium rhodochrous
(which promotes terminal oxidation and acid degradation).731Microbial hy-
droxylation of (-)-A1-THC using Chaetomium globosum occurs in the side-chain
(C-3") and at C-7.732
Two additional cannabidiol pyrolysis products have been identified [one is
(242)733and the other corresponds to cannabidiol with the phenolic and pentyl
720 F. Lotz, U. Kraatz, and F. Korte, 2. Naturforsch., 1978, 33b, 349.
'I2* C. G. Pitt, H. H. Seltzman, Y.Sayed, C. E. Twine, jun., and D. L. Williams, Tetrahedron Letters,
1978, 37.
722 D. B. Uliss, G. R. Handrick, H. C. Dalzell, and R. K. Razdan, Tetrahedron, 1978,34, 1885.
723 M. A. Elsohly, E. G. Boeren, and C. E. Turner, J. Heterocyclic Chem., 1978, 15,699.
724 C.-M. Lee, R. J. Michaels, H. E. Zaugg, A. T. Dren, N. P. Plotnikoff, and P. R. Young, J. Medicin.
Chem., 1977,20,1508.
R. A. Archer, W. B. Blanchard, W. A. Day, D. W. Johnson, E. R. Lavagnino, C. W. Ryan, and J. E.
Baldwin, J. Org. Chem., 1977,42, 2277.
S . Y. Dike and J. R. Merchant, Bull. Chem. SOC. Japan, 1978,51,2145.
B. Yagen, S. Levy, R. Mechoulam, and Z. Ben-Zvi, J. Amer. Chem. SOC., 1977,99,6444; cf. Vol. 3,
p. 89. The numbering of the aromatic ring is incorrectly depicted in a previous Report [Vol. 2, p. 61,
formula (332)l; the numbering of this ring is depicted correctly in formula (240).
728 S.Levy, B. Yagan, and R. Mechoulam, Science, 1978,200, 1391.
729 D. J. Harvey, B. R. Martin, and W. D. M. Paton, Biomed. Mass Spectrometry, 1977, 4, 364.
730 W. Yisak, S. Agurell, J.-E. Lindgren, and M. Widman, J. Pharm. Pharmacol., 1978,30,462; W. A.
Yisak, M. Widman, andS. Agurell, ibid., 1978, 30, 554.
'I3' L. W. Robertson, S.-W. Koh, S. R. Huff,R. K.Malhotra, and A. Ghosh, Experientia, 1978,34,1020.
732 R. M. Christie, R. W. Rickards, and W. P. Watson, Austral. J. Chem., 1978, 31, 1799.
I
OH HO
(242) (243)
groups interchanged, uiz. (243)733"],and the acid-catalysed degradation of A'-

THC has been examined further (cf. Vol. 6, p. 50).734
733 M. Luteyn, H. J. W.
( a ) H. J. W. Spronck and C. A. Salemink, Rec. Truv. chim., 1978,97,185; ( b )J.
Spronck, and C. A. Salemink, ibid.,1978,97, 187; see Vol. 8, p. 63 for earlier work.
734 E. R. Garrett, A. J. Gouyette, and H. Roseboom, J. Pharm. Sci., 1978,67, 27.

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Part I

new section references to all monoterpenoid X-ray crystal structure deter-

2 Physical Measurements: X-Ray Crystallography; Chirality

(1) L1 (2) (3) (4)

Chrysanthernyl Derivatives and Pyrethrins. ( 1R,3R) - ( + )-trans- Chrysanthemic

(8) (9) (10)

34aM.Nakane, C. R. Hutchinson, D. Van. Engen, and J. Clardy, J. Amer. Chem. SOC.,1978,100,7079;

p-Menthanes. (-)-Men thyl trimethylammonium iodide ;39 (-)-men thyl 4 -bromo-

2. Naturforsch., 1972, 27b, 392 (Vol. 5, p. 206).

bromo-6-exo(dimethylaminomethyl)fenchane hydr~bromide;~’ anhydro-

camphenilanic acid p -bromophenacyl ester;79a(k)-carbocamphenilone;” syn -

Spectral and other Physical Data.-The 1: 1 adduct camphor-[Eu(dpm),] illus-

[citral, citronellal, perillaldehyde, myrtenal, menthone, isopulegone, and carvone

Michael-adducts [isopulegone, (1 S)]. '14 y-Shift correlations are of value in

Absolute Configuration, Optical Purity, Asymmetric Synthesis, Resolution.-

A. Hoppmann, P. Weyerstahl, and W. Zummack, Annaien, 1977, 1547.

configurations, 122 discriminating interactions between chiral strat-

with BH3,THF1436or better with BF3,Et20in pentane to the rapid

Chromatography.-G.1.c. papers of interest include the separation of monoter-

menthol isomers,157and further work by Scheffer et al. on the prefractionation of

3 General Synthetic Reactions

16' R. Rossi, Synthesis, 1978, 413.

'71 E. J. Corey and A. K. Long, J. Org. Chem., 1978,43,2208.

trifluoroacetate avoids skeletal rearrangement in the 60% overall conversion of

examined.ls9 Enolates may be converted directly into a -hydroxy-ketones (e.g.

olefinic double bond of a,P -unsaturated carbonyl compounds [e.g. (18)]reports

CH212-Zn-Me3A1.207b Alicyl esters (e.g. bornyl acetate) are reduced to alkanes in

Reductive deoxygenation of alcohols using Ireland’s method212a has been

phenylphosphine-catalysed 1,4-addition of phenyl trimethylsilyl selenide to a,@-

224 D. Liotta, P. B. Paty, J. Johnston, and G. Zirna, Tetrahedron Letters, 1978,5091.

upon the use of lithiated or cuprated species re~pectively.~~’ Regioselective

In the area of functional group protection, pyridinium toluene-p-sulphonate

ylide Me3SiCH=SMe2, generated from methylthiomethyltrimethylsilane

4 Biogenesis, Occurrence, Chemotaxonomy, and Biological Activity

experiments may be complicated by seasonally dependent perturbations of

268 D. V. Banthorpe, B. M. Modawi, I. Poots, and M. G . Rowan, Phytochemistry, 1978,17, 115.

Papers on the biosynthesis of monoterpenoid alkaloids lie outside the scope of

Essential Oils and Chemotaxonomy.-This section reviews the literature of the

275 M. C. Birch, Amer. Scientist, 1978, 66, 409.

artemisia Chenopodium ambrosioides ( a ~ c a r i d o l e )and

Many papers report monoterpenoid analyses with geographical and seasonal

and the other high in 1,8-cineole content),299a new strain of Chenopodium

ponderosa which may prove to be resistant to the pine beetle Dendroctonus

299 R. Grandi, W. Messerotti, and U. M. Pagnoni, Phytochemistry, 1976, 15, 1770.

Chem. (Japan), 1977,41,2205.

Ethyl geranate has been prepared stereoselectively under phase-transfer

reaction with an excess of 2-methylbut-3-en-2-01, catalysed by trifluoroacetic

330 P. J. R. Nederlof, M. J. Moolenaar, E. R. de Waard, and H. 0.Huisman, Tetrahedron,( a ) 1978,34,

produces a lavandulyl carbon Miginiac et ~ 1have. been

is the major product of thermal decomposition of bis-(3,3-dimethylallyl)zinc,

2,6-Dimethyloctanes.-The lack of recent references (only one post- 1963) in a

citronellal, and citronellic acid of R or S configurations in high optical purity [e.g.

Na,CO,-MeOH to yield methyl (E)-3-methyl-7-oxo-oct-2-enoate and straight-

Diels-Alder reaction of itaconic anhydride with cyclopentadiene yields the

responding ipsdienol have been synthesized by vinylcuprate addition to the

[2,3] Sigmatropic rearrangement of ( 5 5 ) , which is formed by thiophilic

Another ortho-ester Claisen rearrangement involves rearrangement of 3 3 -

(PPh3)3]or cobalt octanoate-PPh3-Et3Al as catalysts. With the former Ziegler-

367 Y. Fujita, T. Onishi, and T. Nishida, Synthesis, 1978,532.