?-~crrdwdnu Vol. 42. No. 1 I, pi. 2931 ~2935. 1986 oo404020,!86 13.00+.

00
Pnnvd inGreat Brhn. Pcrymon Journals Ltd.

CHJLi/TiCld: A NON-BASIC AND HIGHLY SELECTIVE

GRIGNARD ANALOGUE

M. T. Rwz,* S. H. KYUNG and M. HGLLMANN

Fachbereich Chemie da UniversitB~_ Hans-Mecrwein-Strasse, D-3550 Marburg, Federal Republic of
Germany

(Receivedin U.S.A. 3 June 1985)

Abstract-Treatment of CHjLi or CH,MgCI with TiCI, results in quantitative formation of CH,TiCI,, a

non-basic reagent which reacts chemo- and stereoselectively with carbonyl compounds. It is considerably
more reaaive than the alkoxy analogue CH,Ti(OCHMe,),. This mums that selective addition lo ketones
[which often react sluggishly with CH,Ti(OCHMe,),] in the presence ofsuch a functionality as nitro, cyano
and ester groups is possible. Addition to enolizable ketones is smooth. The stereoselectivity is comparable lo
that ob&ved for CH,Ti(OCHMeJ,.

INTRODUCTION Upon going to organyltitanium alkoxides

RTi(OCHMe,), or amides RTQNR;),, Lewis acidity is
Despite the usefulness of carbanions in organic
synthesis, a number of problems remain.’ In most cases reduced drastically, so that the above substitution
the reagents are very basic and reactive, which means
processes no longer occur.6*8 In the case of addition to
chiral a-alkoxy aldehydes such as 1, non-chelation
that only a limited number of additional functional
control is possible for the first time. Thus,
groups are tolerated. Furthermore, many carbanions
show a low degree of stereoselectivity in reactions with CH,Ti(OCHMe,), reacts with 1 to form 4 preferen-
carbonyl compounds. tially (3:4 = 8:92). ” So far, no other methyl-metal
reagent has been shown to provide access to the non-
In 1979-1980 we noticed that certain organo-
chelation-controlled manifold. Titanium enolates
titanium(W) reagents behave much more selec-
tively than their Li, Mg or Zn counterpartsze6 having alkoxy or amino groups react similarly.”
These observations led to the general working The size of the amino ligands in RTi(NR;), often
hypothesis that titanation of classical carbanions may aNects the stereoselectivity in reactions with carbonyl
increase the chemo-, regio- and stereoselectivity in compounds. An example is the aldol addition of
reactions with carbonyl compounds and alkyl titanium enolates. *3
halides.7*8 The type of bond formation is not based on
typical transition-metal behaviour such as CO
insertion, oxidative coupling or b-hydride elimin-
ation.P Rather, reaction types traditional to car- I.!
banion chemistry are involved. vn
R = Ma 92 : 8

pkGiq+L; = [ORGANYLknx, 5 R = Et a!397 : a

MgX)
x=qOR,Nt?2
By choosing the proper ligand X at titanium, two
parameters can be varied in a predictable way :8*‘o(1)
the electronic property, e.g. Lewis acidity; and (2) the
steric environment. For example, reagents of the type
RTiCl, are highly Lewis acidic, a property required for
chelation-controlled additions to chiral alkoxy
carbonyl compounds and for substitution reactions
involving &l-reactive alkyl halides. Examples are the
reactions of the parent compound CH3TiC13 (2) with
1” and S4 and the t-alkylation ofthe trichlorotitanium
enolate 8.”
In applying titanium chemistry as delineated here, it
is useful to consider certain physical organic aspects
such as bond energies, structural parameters and
aggregation state. 8*‘oFor example, the Ti-0 bond is
very strong (483 kJ mol-‘), which means that any
reaction leading to such an entity is expected to have a
pronounced thermodynamic driving force. It is also
short (1.7-1.9 A)relative to other metal-ox gen bonds
(Li-O:2.0A;Mg-O:2.1A;Zr-O:2.1 x ).Thishas
an important effect on the stereo- and chemoselectivity
in reactions involving carbonyl compounds.8**0
The present paper is concerned with a simple
reaction, namely the chcmo- and stereoselective
Grignard-type addition of CH,TiCl, (2) to alde-
hydes and ketones. Previously, we had shown that
this reagent discriminates effectively between alde-
hydes and ketones, resulting in complete aldehyde
selcctivity.5 In this respect it is similar to
CH,Ti(OCHMe,),. s*8*10*14*15 However, the chemo-
selective addition of 2 lo &ones in the presence of
additional functional groups remained to be tested.
Such a process would be of synthetic value because
other methyl-metal reagents often fail to provide
acceptable yields of addition products. In fact, even
CH3Ti(OCHMe,), is generally unsuitable for such

2931
2932 M. T. bz
processes: addition to many ketones is so slow that
undesired side reactions involving an additional
sensitive functionality compete.rO.” Thus, a more
reactive, but still selective, reagent is needed. We wish to
report that CH,TiCI, fills this synthetic gap.
RESULTS AND DISCUSSION
Generation and curbonylophilicity ojCH,TiCl,
CHJTiCIj can be prepared in dichloromethane by
the reaction of (CH,),Zn with TiCl,.3 Such ether-free
solutions are needed for the SN1 substitutions as well
as the chelationcontrolled additions described in
the introductory remarks. However, for the present
purpose, a more convenient procedure is possible.
Ethereal solutions of CHSLi or CH,MgCl are simply
treated with the equivalent amount of TiC1,.16*‘7
(C+)2Zn
Compound 2 exists in equilibrium with the mono-
etherate 13 and the bis-etherate 14.‘”
Typically, an ethereal solution ofCH,Li (one part) is
‘2 14
added to TiCI, (one part) in ether at -78” and the
solution allowed to come to about - 30”. Titanation is
essentially quantitative, as judged by the reactions
with carbonyl compounds. For example, addition
of benzaldehyde (15) or 2-heptanone (17) results in
quantitative addition. Following aqueous workup, the
crude products consist of _ 98% of 16 and 18,
respectively.
PhCHO
!. _ k
-3dC& h Ph
‘2
‘3
Zh
‘2
Addition to aldehydes is quite fast at - 30”, unlike the
ketone addition reaction. The latter is best performed
by letting the temperature come to - 5 or 0”. Generally,
room temperature should be avoided because tar
formation may occur. i6 This is probably due to the fact
that the tertiary trichlorotitanium alcoholate under-
goes S,l-like ionization, followed by proton elimin-
ation and oligomerization of the olefin. In the above
and in the following reactions, the reagent prepared
from CH,Li and TiCl, is symbolized by 2, although 13
or 14 (or all three) may actually be the reacting
speciesi
Aldehyde-ketone discrimination
The above observations suggest that the reagent
CH,Li/TiClJOEt, should react aldehyde-selectively
in the presence of ketones, despite the fact that it is
et al.
considerably more reactive than the alkoxy analogue
CH,Ti(OCHMe,),. In fact, we had previously
demonstrated aldehyde-selectivity for 2 prepared from
dimethylzinc and TiCl, in dichloromethane.4 We were
therefore not surprised to discover that this also holds
for CH,LifliCl, in ether. Noteworthy is the
observation that CHJLi alone (or CHsMgCl) reacts
almost chemo-randomly;**‘O in these cases side
reactions such as aldol additions involving the ketone
and the aldehyde also occur to some extent.
0
PhCHO l K -T&iT
m
Why are titanium reagents more selective than the Li,
Mg andeven Zr analogues? Resides possible electronic
effects (e.g. C-metal bond polarity), we believe that
steric factors are involved.*~‘O The Ti-0 bond is
considerably shorter than other metal-oxygen bonds,
which means that in the transition state of carbonyl
addition. reagent and substrate are tightly together.
Thus, small steric differences between two potential
acceptor sites are “felt”. Even ketonoketone discrimi-
nation is possible (see below).
Reactions of aldehydes having additional functional
groups
A few aldehydes having an additional functionality
were tested. Nitro, cyan0 or ester groups do not
interfere with carbonyl addition. These and similar
aldehyde addition reactions are also possible using
CH,Ti(OCHMe,),. a*i’ However, it was necessary to
show that 2, being more reactive, performs just as well.
2,
0) X - C@Et
b) X=CN
d X= NO2
Addition to enolizable ketones
Grignard and alkyllithium reagents are very basic,
which means that reactions with readily enolizable
ketones fail to provide acceptable yields of addition
products. This also applies to the parent methyl
compound. In order to test whether titanation with
TiCl, solves this problem, 2 was reacted with ketones
25,27 and 29. In all cases the crude products contained
> 90% of the desired adduct. The yields shown
in parentheses refer to pure isolated carbinols ; the ac-
tual isolation was not optimized. The results demon-
strate the superiority of CH3TiC13 relative to
CH3Ti(OCHMe2)J, which reacts with 29 to provide
< 20% of 30.
The CH,Li/TiClJether reagent is cheaper and
more readily available than CH,CeC12*0 and
CH3Zr(OR),,‘i which also react smoothly with
enolizable ketones. The CH,MgCl/TiCl, combination
is just as efficient as CH,Li/TiCl.. For example, the
yield of30 is 9 1%. A limitation ofthe present procedure
 CH,Li:TiCI, : a non-basic and highly selective Grignard analoguc 2933

reacts completely chemo- and stereoselectively. The

R
WA @C& Ph&”
crude product contains only adduct 45, which can
2s Is (m oh) be isolated in pure form to the extent of 91%.
(CH&Ti(OCHMe,), behaves similarly, but again
only one methyl group is utilized. l 5

lo ,-o(90 %)

pertains to the reaction of 2 with cyclic aryl ketones

such as n-tetralone.16 Addition occurs but a great deal
of tar is formed. It should be noted that CH,Li alone
reacts smoothly with a-tetralone. i.e. it poses no
enolization problems!’

Ketone-ketone discrimination
We have previously shown that CH,Ti(OCHMe,),
is capable of a surprising degree of discrimination
between two different ketones, although long reaction
times are generally needed and conversion is often
mediocre. The following reactions demonstrate that 2
can also distinguish between two different ketone sites.
The advantage over CH,Ti(OCHMe,), has to do with Lc r_S(91 %I r_B
greater reactivity and thus short reaction times as well >99 : ‘1

as better yields (essentially quantitative conversion).

Equatorial versus axial addition to substituted
cyclohexanones
The question of equatorial versus axial addition to
cyclic ketones has been addressed on numerous
occasions.a3 In the case of six-membered rings,
conformationally locked 4-t-butylcyclohexanone (47)
has often served as a model compound. Of all the
reagents tested so far, CH,Ti(OCHMe& represents
the best choice, the ratio of axial to equatorial alcohol
(48:49)dependingupon thereactionconditions(82: 18
in the case of CH2C12 at 22”; 86: 14 in ether at 22” ;
89: 11inetherat0°;94:6inn-hexaneat -15t022°0ver
a period of 24 h. s~*.14.24
Thus, the best result (94: 6)*’
Reactions with ketones having additional jiunctional is comparable to that observed for 2CH,Li/LiCIO12’
groups or CH,Li/(CH,),CuLi. 26The latter reactions require
The following reactions demonstrate that addition an excess of active methyl groups.
to ketones in the presence of such a functionality as
nitro, cyano and ester groups poses no problems.
Interestingly,CH,MgXisknowntoreactwiththenitro
ketone 35 solely at the aryl ring.” Thus, titanation of
the Grignard reagent with TiCl, alters the chemical
behaviour completely. Here again, it makes no
difference whether CHSLi/TiC1, or CH,MgCl/TiCl, is
used. The yield of 36 is essentially identical in both
cases. The aliphatic nitro compound 38 also reacts
smoothly with 2. In contrast, CH,Ti(OCHMe2), 68 : q or%
affords only 15% of 39 after a reaction time of 2 days at
room temperature. ‘*I5 The reason for this has to do Reagent 2 was reacted with 47 at 0”/3 h, resulting in
with the fact that competing reactions at the nitro an isolated yield of 92% of addition products, but the
moiety occur, probably deprotonation at the a- diastereomer ratio 48: 49 turned out to be a
position. This problem was originally solved by using disappointing 71: 29. At -20” diastereoselectivity
the more reactive (CH,)2Ti(OCHMe2)1.8*1’ However, improved to 80:20. Thus, CH,Ti(OCHMe,), is the
since only one active methyl group is utilized, the reagent of choice.
present procedure employing CHILi/TiCld is certainly In the case of 2- and 3-substituted cyclohexanones, 2
to be preferred. The pronounced difference between can compete effectively with CH,Ti(OCHMe,),. For
CH,Ti(OCHMe,), and 2 is also apparent in the example, 50 is converted into an 88: 12 mixture of
reaction of the keto-ester 42. Whereas the latter affords 51 and 52, respectively (isolated yield 94%). This
an excellent yield of 43, CH,Ti(OCHMe,), (22”/12 h) is comparable with the result obtained using
leads to 55% of the corresponding lactone.’ 5 Finally,44 CH,Ti(OCHMe,), (89: 11 ratio).8*24 CH,MgI de-
2934 M. T. Rrm
livers a 54:46 product mixture.23 As noted above, 2
adds to the 2-substituted cyclohexanone 44 with
complete chemo- and stereoselectivity. Thus, in all the
cases observed so far, equatorial attack is preferred. The
traditional explanation is applicable in the present
case : 1,3-non-bonded interactions (in the case of axial
attack)aremoresevere than torsionaleffects(in thecase
of equatorial attack).23
l,2-Asymmetric induction
The Cram/anti-Cram problem remains to be solved
satisfactorily in a general way. 2-Phenylpropanal(53)t
has been widely used to study l&asymmetric
induction in addition reactions of chiral carbonyl
compounds.27 Following Cram’s report that
CH,MgBr forms a 66:34 mixture of 54 and 55,”
respectively, other methyl-metal compounds were
tested. However,“milder” reagents such as CH,CdX or
CH,ZnX fail to increase diastereoselectivity (54:55
z 60:40).28 CH,Li is slightly better (54:55 70:30 at
- 10” and 75: 25 at -60”).29
53
B
90 :
:}92%
Titanation of CH,MgCl or CH,Li improves the
situation considerably. In the early phase ofour work in
the area of organotitanium chemistry, we showed that
CH,Ti(OCHMeJ, leads to an unprecedented dia-
stereomer ratio of 88: 12 (at -40”) in favour of
the Cram product 54.5 Later, further improvement
was attained by the use of the triphenoxy deriva-
tive CH,Ti(OPh)J (54: 55 = 93 : 7).24 In contrast,
CH,TiCl, (prepared from dimethylzinc and TiCl, in
dichloromethane) turned out to be somewhat less
selective (81 : 19 diastereomer ratio).5*24 The THF
analogue of 14 (prepared from dimethylzinc and TiCl,
in THF) leads to an 85: 15 mixture, but related
octahedral complexes are slightly less selective
(- 82 : 18 ratios). l9 These numbers are all rather
similar, which seems to suggest that the octahedral
complexes are not the reacting species.19 Rather,
dissociation to the penta-coordinate complex or even
the free CH,TiCI, may well precedecarbonyl addition.
In view of ttie above results, we were somewhat
surprised to discover that the combination
CH,Li/lKl,/OEt, leads to a 54:55 ratio of 90: 10
(-65”/4 h ; 92% yield). This speaks against the
involvement of free CHsTiCI,. Although mechanistic
ambiguities remain to be cleared up (including the
possible role of salt effects), participation of 13 seems
reasonable. This does not mean that the other two
species are not involved to some extent. From a
synthetic viewpoint, it is important to note that the
THF analogue of 14 is considerably less reactive. For
example, CH,LifliCl, in THF (as the solvent) reacts
sluggishly with ketones. l6 THF is a better donor than
ether, making the octahedral complex more stable and
less prone to dissociate.
~Onlyoneenantiomericformisarbitrarilyshown although
a raoemate was used, leading to raccmic products.
ef al.
CONCLUSIONS
The titanation of CH,Li or CHsMgCl in ether is a
convenient source of CH,TiCI,. It is a non-basic and
highly selective Grignard analogue. Its prime virtue
relative to the alkoxy analogue CH,Ti(OCHMe2)S
pertains to its higher reactivity towards ketones. This
makes chemosclective addition to ketones possible in
the presence of an additional sensitive functionality, a
process that is often inefficient or impossible using
CH,Li, CH,MgCl or CHJTi(OCHMe2)3. Stereo-
selectivity of CH,TiCl, is comparable to that of
CH,Ti(OCHMe,),, although in certain cases the latter
is definitely the reagent of choice. An example is the
non-chelation-controlled addition to chiral a-alkoxy
aldehydessuch as 1.” CH,Li/TiCl,/OEt2 is unsuitable
for such a reaction; it leads to a 60:40 ratio of 3:4.16
This again is not in line with thesole involvement offree
CH,TiCIB. In order to achieve effective chelation
control, CH,TiCI, in dichloromethane (free of ether)
must be used.’ 1Recently, other uses ofCH,TiCl, have
been reported,3o including stereoselective reactions of
chiral acetals.31
EXPERIMENTAL
General in,fkmation. AU reactions were performed in dry
flasks under an atmosphere of N,. Solvents were dried
according to standard te-chniques. Product ratios were
determined using a Perkin-Elmer EM 960 gas chromato-
graph (capillary column), an internal standard being present
in the mixture. In all cases, the products were identified by
comparison with authentic samples.
Typical procedure for the preparation and reaction of
CH ,TiCl, (2). TiCI, (I .9 g. IO mmol) was added by syringe to
about 50 ml of cooled (-78”) Et,O. resulting in partial
precipitationoftheyellowTiC1,-bisctherate.An~he~alsoln
of MeLi (10 mmol) was added slowly, which caused a colour
change to dark black-purple. The mixture was allowed to
come to - 50” or - 30”. and a carbonyl compound was then
added (e.g. 15, 17,23,27.29,35.40,42,44,47, SO,53). After
reacting for the proper length of time (as indicated in the text),
thecold soln (it should not be allowed to reach room temp) was
poured into H,O. In rare cases a TiO,containing emulsion
may form, in which case a sat soln of NH,F should be
employed. Following usual workup (Et,0 extraction,
washing with H,O, drying over MgSO,), the products
were isolated by standard techniques, generally Kugelrohr
distillation.
In thecaseofsensitivepolyfunctionalmolecules(e.g.JS),it is
better toadd thecoldsolttof2 toan Et,Osoln ofthecarbonyl
component. This reversed mode of addition serves to ensure
maximum chemoselectivity. This procedure was applied in
competition experiments involving carbonyl pairs. In these
cases it is important to use theexact amount ofreagent because
even a slight excess falsifies the results. For this reason, about
3-S% less of the titanium reagent should be used.
InplaccofCH,Li,anetherealsolnofCH,MgClcanalsobe
employed.In thecaseswhich were tested,nodiffereneerelative
to CH,Li/TiCl, was detected. Also, instead of suspending the
TiCI,inEt,OandthenaddingCH,LiorCH,MgCl.TiCl,can
be dissolved in CHICll followed by the usual procedure.
Several carbonyl additions were performed using both
solvents,andnodiITerencesinthefinal result wercobserved.‘6
Acknowledgement-This work was supported by the
Fonds der Chemischen Industrie and the Deutsche
Forschungsgemeinschaft.
REFERENCES
“J. C. Stowell, Carbanions in Organic Synthesis. Wiley, New
York (1979); ‘R. B. Bates and C. A. Ogle, Carbanfon
Chemistry. Springer, Berlin (1983).
 CH,LifliCI, : a non-basic and highly selective Grignard analogue
2Fint reported in lectures presented at the University of
Munich (10 November 1979), Bayer-AC in Krefeld (15
November 1979) and at the Max-Planck-lnstitut fiir
Kohleforschunn in Miilheim (10 December 1979).
3M. T. Reetq J. &termann and R. Steinbach, Angew. Chem.
92.931 (1980): Anaew. Chem. Int. Ed. Enal. 19.900(1980).
’ MIT. Ret&J: iVesiermann and R. Stein&h, &nv.‘Cher;r
92933 (1980); Angew. Chem. Inc. Ed. Engl. 19.901(1980).
‘M. T. Reetz, R. Steinbach. J. Wcstermann and R. Peter,
Angew. Chem 92.1044 (1980); Angew. Chem. Inc. Ed. Engl.
19, 1011 (1980).
6 M. T. Reek B. Wenderoth, R. Peter, R. Steinbach and J.
Watcnnann, J. Chem. Sot. Chem. Co-n. 1202 (1980).
‘M. T. Reetz, R. Steinbach, B. Wenderoth and J.
Westermann, Chem. Ind. 541(1981).
* M. T. Reetz, Top. Curr. Gem. 106,1(1982).
9ES. G. Davies, Organorransition Metal Chemisrry:
Applicolion 10 Organic Synthesis. Pergamon Press, Oxford
(1982) ; bE. Negishi, Organometallics in Organic Synthesis.
Wiley, New York (1980); ‘J. P. Collman and L. S. Hegedus,
Principles and Applicarions of Organotransilion Metal
Chemistry. University Science Books, Mill Valley,
California (1980).
ItiM. T. Ratz. Organotimnium Reagents in Organic Synthesis.
Springer, Berlin (1986) ; bM. T. Re-etz, Pure Appl. Chem. 57.
1781 (1985).
““M. T. Ratz. K. Kesseler, S. Schmidtberger. B. Wenderoth
and R. Steinbach. Angew. Chem. 95, 1007 (1983); Angew.
Chem. fnt. Ed. Engl. 22.989 (1983); Angew. Chem. Suppl.
ISI I (1983). *Forareviewofchelation-andnon~helation-
controlled additions to chiral alkoxy carbonyl compounds
see : M. T. Ratq Angew. Chem %,542( 1984); Anger. Chem.
Inr. Ed. Engl. 23,556 (1984).
120M.T. Ratz, W. F. Maier. I. Chatziiosifldis, H. Giannis, H.
HeimbachandU.tiwe,Chem.Ber. 113.3741(198O);*M.T.
Ratq 1. Chatziiositidis, F. Hiibner and H. Heimbach. Org.
Svnfh. 62. 95 11984). ‘Evidence for the intermediacy of
thchlorotitani;m Aolates: M. T. Reetz, Nachr. Chem
Techn. Lab. 29. 165 (1981); H. Heimbach, Diploma&it,
Universitlt Bonn (1980). ‘Review of a-alkylation of en01
silanes using S,l-reactive alkyl halides : M. T. Raw Angew.
Chem. 94, 97 (1982); Angew. Chem. Int. Ed. Engl. 21, 96
(1982).
l3 M.T. Ratzand R. Peter, Tetrahedron Lett. 22,4691(1981).
“B. Weidmann and D. Seebach, He/v. Chim. Acta 63.2451
(1980).bReview: B. Weidann and D. Seebach, Angew. Chem.
95.12 (1983); Angew. Chem. Int. Ed. Engl. 22,31(1983).
2935
I’ M. T. Ratz, J. Westermann, R. Steinbach, B. Wendcroth, R.
Peter, R. Ostarek and S. Maus, Chem. &r. 118,1421(1985).
16S. H. Kyung, Dissertation, Universitlt Marburg (1985).
*“CH,TiCI,wasfintsynthcsizedinordertotatitsactivityin
Ziegler-Natta type polymerization : C. Beemxun, Angew.
Chem. 71. 195 (1959). ‘General reviews of organotitanium
compounds : ~Tira&@.sche Vwbind&en, Gmelin
Hand6uch.Part1(1977).Part2(1980).Part3(1984).Part4
(1984);Galso M:Bo&ll. P.D:Gav&s, J. WiKellandand
J. McMakin& Comprehensiw Organomeldlic Chemisrry
(Edited by G. Wilkinson, F. G. A. Stone and E. W. Abel).
Chap. 22. Pergamon Press, Oxford (1982).
l&K. H. Thiele and P. Zdunneck, Z. Chem. (Leipzig) 10,152
(1970). bConceming the THF adduct of CHITiCI,. se-e:
G. W. A. Fowles, D. A. Rice and J. D. Wilkins. J. C&m.
Sot. A 1920(1971).
I9 M. T. Ratz and J. Westermann, Synch. Co-n. 11, 647
(1981).
“T. Imamoto, Y. Sugiura and N. Takiyama, Tetrahedron
Left. 25.4233 (1984).
2’oM. T. Ratq R. Steinbach, R. Urz, B. Wenderoth and R.
Peter, Angew. Chem. 94,133 (1982); Angew. Chem. InI. Ed.
Engl. 21, 135 (1982); Anger. Chem. Suppl. 257 (1982); bB.
Weidmann, C. D. Maycock and D. Seebach, He/u. Chim.
Acla 64, 1552 (1981).
l2 G. Bartoli. M. Bosco and R. Dalpouo, Tetrahedron Left. 26,
115 (1985).
23E. C. Ashby and J. T. Laemmle. Chem. Rev. 75,521 (1975).
2*M. T. Ratz, R. Steinbach, J. Westermann. R. Peter and B.
Wenderoth, Chem. Bw. 118, 1441(1985).
*’ E. C. Ashby and S. A. Noding, J. Org. Chem. 44.437 1 ( 1979).
26T. L. Macdonald and W. C. Still,J. Am. Chem. Sot. 97.5280
(1975).
170D.J. Cram and F. A. Abd Elhafez, Ibid. 74. 5828 (1952);
bJ. D. Morrison and H. S. Masher. Asymmetric Or.qanic
Reucrions. Prentice-Hall. Englewood ClilTs, New Jcrse.y
(1971); ‘P. A. Bartlett, Tenahedron 36.3 (1980).
‘s P. R. Jones, E. J. Goller and W. J. KauRinan, J. Org. Chem.
36.3311(1971).
29M T. Reetzand J. Maricincik. unpublished results.
3oT.‘Kaulfmann, R. AbeIn and D. Wingbehrmiihle, Angew.
Chem. %, 724 (1984); Angew. Chem. Int. Ed. Engl. 23,729
(1984).
J’*S D .Lindell. J. D. Elliott and W. S. Johnson, Terrahedron
Ln.‘ts. 3947 (1984): *A. Mori. K. Maruoka and H.
Yamamoto, Ibid. 25, k421 (1984).