Protective Groups in Organic Synthesis, Third Edition. Theodora W. Greene, Peter G.M.

Wuts
Copyright  1999 John Wiley & Sons, Inc.
ISBNs: 0-471-16019-9 (Hardback); 0-471-22057-4 (Electronic)

10
REACTIVITIES, REAGENTS,
AND REACTIVITY CHARTS

REACTIVITIES

In the selection of a protective group, it is of paramount importance to know the

reactivity of the resulting protected functionality toward various reagents and
reaction conditions. The number of reagents available to the organic chemist is
large; approximately 8000 reagents are reviewed in the excellent series of books
by the Fiesers.’ In an effort to assess the effect of a wide variety of standard
types of reagents and reaction conditions on the different possible protected
functionalities, 108 prototype reagents have been selected and grouped into 16
categories:*

A. Aqueous
B. Nonaqueous Bases
C. Nonaqueous Nucleophiles
D. Organometallic
E. Catalytic Reduction
F. Acidic Reduction
G. Basic or Neutral Reduction
H. Hydride Reduction
I. Lewis Acids
J. Soft Acids
K. Radical Addition
701
702 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

L. Oxidizing Agents
M. Thermal Reactions
N. Carbenoids
0. Miscellaneous
P. Electrophiles

These 108 reagents are used in the Reactivity Charts that have been prepared for
each class of protective groups. The reagents and some of their properties are
described on the following pages.

REAGENTS

A. AQUEOUS

1. pH< 1, 100’ Refluxing HBr

2. pH<l 1 NHCl
3. pH1 0.1 NHCl
4. pH 2-4 0.01 N HCl; l-0.01 NHOAc
5. pH4-6 0.1 N H,BO,; phosphate buffer;
HOAc-NaOAc
6. pH 6-8.5 H20
7. pH 8.5-10 0.1 N HCO,-; 0.1 N OAc-; satd.
CaCO,
8. pH lo-12 0.1 N C032-; l-0.01 N NH,OH;
0.01 N NaOH; satd Ca(OH),
9. pH>12 l-0.1 N NaOH
10. pH> 12,150’

B. NONAQUEOUSBASES
11. NaH
12. m--M3C~a pK = 32
13. [C,,H,j- Na’ l
pK’: G 37
14. CH,SOCH,-Na’ pK = 35
15. KO-t-C,H, PK I= 19
16. LiN( X,H,), (LDA) pKc, =36
17. Pyridine; Et,N PK N= 5; 10
18. NaNH,; NaNHR PK u - 36

C. NONAQUEOUSNUCLEOPHILES

19. NaOCH,/CH,OH, 25’ PK a= 16

20. Enolate anion PK u-- 20
2 1. NH,; RNH,; RNHOH PK a-- 10
 REAGENTS 703

22. RS-; N,-; SCN-

23. OAc-; X- pK, = 4.5
24. NaCH, pH 12
25. HCN, cat. CN-, pH 6 pK, = 9. For cyanohydrin formation

D. ORGANOMETALLIC

26. RLi
27. RMgX
28. Organozinc Reformatsky reaction. Similar:
R,Cu; R,Cd
29. Organocopper R,CuLi
30. Wittig; ylide Includes sulfur ylides

E. CATALYTIC REDUCTION

3 1. HJRaney Ni
32. H,/Pt, pH 2-4
33. HJPd-C
34. H,/Lindlar
35. HJRh-C or Avoids hydrogenolysis of
H,/ Rh-Al,O, benzyl ethers

F. ACIDIC REDUCTION

36.Zn/HCl
37.Zn/HOAc; SnClJHCl
38. Cr(II), pH 5

G. BASIC OR NEUTRAL REDUCTION

39. Nail NH,

40. Al(Hg)
41. SnClJPy
42. H;S or HSO,-

H. HYDRIDE REDUCTION

43. LiAlH,
44. Li-s-Bu,BH, -50° Li-Selectride
45. [(CH,),CHCH(CH,)],BH Disiamylborane
46. B,H,[ 0’
47. NaBH,
48.Zn(BH,), Neutral reduction
49. NaBH,CN, pH 4-6
50. (l’-C,H,),AlH, -60’ Dibal
5 1. Li(O-t-C,H&AlH, 0’
704 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

I. LEWIS ACIDS (ANHYDROUS CONDITIONS)

52 . AlCl?, 80°
53 . AlCl,, 25’
54 . SnCl,, 25”; BFjaEt,O
55 . LiClO,; MgBr, For epoxide rearrangement
56 . TsOH, 80° Catalytic amount
57 . TsOH, O” Catalytic amount

J. SOFT ACIDS

58 . Hg (11)
59 . f%(I)
60 . Cu(II)/Py For example, for Glaser coupling

K. RADICAL ADDITION

61 . HBr/initiator “Acidic” HX addition; acidity = TsOH, O”

62. HX /initiator Neutral HX addition; X = P, S, Se, Si
63. NBS/Ccl,, hvor heat Allylic bromination
64. CHBr,; BrCCl,; CCl,/In Carbon-halogen addition

L. OXIDIZING AGENTS

65. 0~0,
66. KMnO,, O”, pH 7
67. 0,, -50’
68. RCO,H, O” Epoxidation of olefins; prototype for
H,O,/H+
69. RCO,H, 50° Baeyer-Villiger oxidation of hindered
ketones
70. CrOJPy Collins oxidation
71. CrO,,pH 1 Jones oxidation
72. H,O,/OH-, pH lo-12
73. Quinone Dehydrogenation
74. lo, Singlet oxygen
75. CHSOCH,, 100’ (DMSO); HCO,- may be added
to maintain neutrality
76. NaOCl, pH 10
77. Aq. NBS Nonradical conditions
78. I,
79. C,H,SCl; C,H,SeX
80. Cl,; Br,
8 1. MnO, /CH,Cl,
82. NaIO,, pH 5-8
83. SeO,, pH 2-4
84. SeO, /Py In EtOH/cat. Py
 REACTIVITY CHARTS 705

85. K,Fe(CN),, pH 7-10 Phenol coupling

86. Pb(IV), 25O Glycol and a-hydroxy acid cleavage
87. Pb(IV), 80° Oxidative decarboxylation
88. Tl(NO,),, pH 2 Oxidative rearrangement of olefins

M. THERMAL REACTIONS

89. 150° Some Cope rearrangements and

Cope eliminations
90. 250° Claisen or Cope rearrangement
91. 350° Ester cracking; Conia “ene” reaction

N. CARBENOIDS

92. :CCl,
93. N$HCO,C,H,/Cu, 80’
94. CHJ, / Zn-Cu Simmons-Smith addition

0. MISCELLANEOUS

95. n-Bu,SnHlinitiator
96. Ni(C0)4
97. CH,N,
98. SOCl,
99. Ac,O, 25’ Acetylation
100. Ac,O, 80’ Dehydration
101. DCC Dicylohexylcarbodiimide,
C,H,,N=C=NChH,,
102. CH,I
103. (CH,),O+BF,-
_- Or CH,OSO,F=Magic Methyl:
SEVERE POISON
104. 1. LiN-i-Pr,; 2. Me1 For C-alkylation
105. 1. K,CO,; 2. Me1 For O-alkylation

P. ELECTROPHILES

106. RCHO
107. RCOCl
108. C’ion/olefin For cation-olefin cyclization

REACTIVITY CHARTS
One requirement of a protective group is stability to a given reaction. The charts
that follow were prepared as a guide to relative reactivities and thereby as an aid
in the choice of a protective group. The reactivities in the charts were estimated
706 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

by the individual and collective efforts of a group of synthetic chemists. It is

important to realize that not all the reactivities in the charts have been deter-
mined experimentally and considerable conjecture has been exercised. For those
casesin which a literature reference was available concerning the use of a pro-
tective group and one of the 108 prototype reagents, the reactivity is printed in
italic type. However, an exhaustive search for such references has not been
made; therefore, the absence of italic type does not imply an experimentally
unknown reactivity.
There are four levels of reactivity in the charts:
“H” (high) indicates that under the conditions of the prototype reagent, the
protective group is readily removed to regenerate the original functional group.
“M” (marginal) indicates that the stability of the protected functionality is
marginal and depends on the exact parameters of the reaction. The protective
group may be stable, may be cleaved slowly, or may be unstable to the condi-
tions. Relative rates are always important, as illustrated in the following exam-
ple5 (in which a monothioacetal is cleaved in the presence of a dithiane), and
may have to be determined experimentally.

.’ Me

k’SiMe2-t-Bu

“L” (low) indicates that the protected functionality is stable under the reaction
conditions.
“R” (reacts) indicates that the protected compound reacts readily, but that the
original functional group is not restored. The protective group may be changed
to a new protective group (eq. 1) or to a reactive intermediate (eq. 2), or the pro-
tective group may be unstable to the reaction conditions and react further (eq. 3).

H, I Pd-C
( 1) ROCOC6H4-p-NO, w ROCOC6H4-p-NH2
 REACTIVITY CHARTS 707

MeJO+ BF,-
(2) RCONR’, - b [RC=N+R’2 BF4--]
I
OMe

(3) RCH( OR’), pHc19 ‘Ooo+ [RCHO] -p+ condensation products

The reactivities in the charts refer only to the protected functionality, not to
LDA ~ : “y
atoms adjacent to the functional group; for example, RCOOEt
(low) reactivity of PG(Et). However, if the protected functionality is
R,CHCOOEt, this substrate obviously will react with LDA. Reactivity of the
entire substrate must be evaluated by the chemist.
Five reagents [#25: HCN, pH 6; #88: Tl(NO,),; #103: Me,O’BF,-; #104:
LiN-i-Pr,lMeI; and #105: K,CO,/MeI] were added after some of the charts had
been completed; reactivities to these reagents are not included for all charts.
The number used to designate a protective group (PG) in a Reactivity Chart is
the same as that used in the body of the text in theflrst edition.
Protective group numbers in the Reactivity Charts are not continuous, since
not all of the protective groups described in the text are included in the charts.
The protective groups that are included in the Reactivity Charts are, in general,
those that have been used most widely; consequently, considerable experimental
information is available for them.
The Reactivity Charts were prepared in collaboration with the following
chemists, to whom we are most grateful: John 0. Albright, Dale L. Boger,
Dr. Daniel J. Brunelle, Dr. David A. Clark, Dr. Jagabandhu Das, Herbert
Estreicher, Anthony L. Feliu, Dr. Frank W. Hobbs, Jr., Paul B. Hopkins, Dr.
Spencer Knapp, Dr. Pierre Lavallee, John Munroe, Jay W. Ponder, Marcus A.
Tius, Dr. David R. Williams, and Robert E. Wolf, Jr.

’ L. F. Fieser and M. Fieser, Reagents for Organic Synthesis, Wiley-Interscience, New York,
1967, Vol. 1; M. Fieser and L. F. Fieser, Vols. 2-7, 1969-1979; M. Fieser, Vols. 8-17,
1980-l 994.
2 The categories and prototype reagents used in this study are an expansion of an earlier set of
11 categories and 60 prototype reagents,” originally compiled for use in LHASA4 (Logic and
Heuristics Applied to Synthetic Analysis), a long-term research program at Harvard
University for Computer-Assisted Synthetic Analysis.
3 E. J. Corey, H. W. Orf, and D. A. Pensak, .I. Am. Chem. Sot., 98,210 (1976).
4 Selected references include E. J. Corey, Quart. Rev., Chem. Sot., 25,455 (197 1); H. W. Orf,
Ph. D. Thesis, Harvard University, 1976.
5 E. J. Corey and M.G. Bock, Tetrahedron Lett., 2643 (1975).
708 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

Reactivity Chart 1. Protection for Hydroxyl Group: Ethers

1. Methyl Ether
2 . Methoxymethyl Ether (MOM)
3 . Methylthiomethyl Ether (MTM)
6 2-Methoxyethoxymethyl Ether (MEM)
8: Bis(2-chloroethoxy)methyl Ether
9 Tetrahydropyranyl Ether (THP)
11: Tetrahydrothiopyranyl Ether
12. 4-Methoxytetrahydropyranyl Ether
13. 4-Methoxytetrahydrothiopyranyl Ether
15. Tetrahydrofuranyl Ether
16. Tetrahydrothiofuranyl Ether
17. 1-Ethoxyethyl Ether
18. 1-Methyl- 1-methoxyethyl Ether
21 . 2-(Phenylselenyl)ethyl Ether
22. t-Butyl Ether
23. Ally1 Ether
26. Benzyl Ether
28 . o-Nitrobenzyl Ether
35 . Triphenylmethyl Ether
36. wNaphthyldiphenylmethy1 Ether
37 p-Methoxyphenyldiphenylmethyl Ether
41: 9-(9-Phenyl- lo-oxo)anthryl Ether (Tritylone)
43 Trimethylsilyl Ether (TMS)
45: lsopropyldimethylsilyl Ether
46. t-Butyldimethylsilyl Ether (TBDMS)
48. t-Butyldiphenylsilyl Ether
51. Tribenzylsilyl Ether
53. Tri isopropyl si 1yl Ether

(See chart, pp. 709-711.)

Reactivity Chart 1. Protection for the Hydroxyl Group: Ethers

+ +
.,$ P cy
% 2 ii a: =m
d 5 8 :I 2’ “, f
0 b
9 ; -h3k(d
11 12 13 14 15 16 17 18 .9 20 21 22 23 24 25 26 27 28 29 30 11 32 33 34 35 B6 37 38
B. BASIC c. NucLmPH1L1C D.OlGA-. E. CAT. REDM. P.
i BMLLLLLLL L LLLLLLLL LLLLLLL L L L L L L L L L L L L L
2 HHBMLLLLL H LLLLLLLL LLLLLLL L L L L L LML L L HHL
3 HEMLLLLLL M LMRMLHLL LLLLLLL L L L L L R RRL R RRM
6 HHLLLLLLL L LLLLLLLL LLLLLLL L L L L L L LL LL nLL
8 HHHHMLLLM H LRRRRRLR RRMRLR R RMR L R RRLL HHM

9 HHBHMLLLL L LLLLLLLL LLLLLLM L L L L L L H L L L

H HM
11 HHHHLLLLL M LMRRLMLL LLLLLL L L L L L R RRL R HHM
12 HHHHMLLLL L LLLLLLLL LLLLLL L L LL L LH L L L H HM
13 HHHHMLLLL M LLMLLLLL LLLLLL ML L L L R RRL R HHM
15 HHHHHLLLL L LLLLLLLL LLLLLL L L L L L L HL LL HHH

16 HHHMLLLLL M LMRRLMLL LLLLLL L L L L L R RR L R HHM

17 HHBHLLLLL L LLLLLLLL LLLLLL L L L L L L H L L L H HL
18 HHHHMLLLL L LLLLLLLL LLLLLL L L L L L L H L L L H HM
21 HHMLLLLLL hf LRRRMRLR MLLRLL R L L L L RR R L R H HM
22 HHLLLLLLL L LLLLLLLL LLLLLLL L L L L L L L L L L LL L

23 HHLLLLLLM R LLLLRLLL RLLLLLL L L L L L RR R L B L L L

26 HHLLLLLLL L LLRLLLLL LLLLLLL L L L L L H H H LL L L L
28 HHLLLLLLL /'I RMRRLRLR LLLLLLL M RR R L H H H L R RR R
35 HHHHLLLLL L LLHLLLLL LLLLLL L L L L L H HH L L H HL
36 HHHHLLLLL M LLHLLLLL LLLLLL L L L L L H H H L L HHL

37 HHHHMLLLL L LLHLLLLL LLLLLL L L L L L H HH L L H HM

61 HHLLLLLLL L LLRLLLLL LMRLLL R R R L R R RR L R RR R
43 HHHHHHHHH H HHHHLLLH HLHHLHH H H L L L L HHLL H H H
45 HHHHMLLLH H LLLLLLLL LLLLLLL HH L L H M HML L H HM
46 HHHHLLLLH H LLLLLLLL LLLLLL L L L L L L H L LL H L L

G8 HMMLLLLtH H LLLLLLLL LLLLLL L L L L L L L L L L ML L

51 HHHHLLLLH H LLHLLLLL LLLLLL L L L L L L H L L L HH L
53 HHHHLLLLH H LLLLLLLL LLLLLL L L L L L L H L L L H H L
-
Reactivity Chart 1. Protection for the Hydroxyl Group: Ethers (Continued)
9
4 X
zm 2 2
CJX *
2 “0
ws <z 2 2PO
5 ;I x2 lil g $j g g g’

33 s?> P 4 g 2413

PG 39 40 41 42 13 44 45 46 47 48 49 SO 51 i2 53 54 55 56 5i 58 59 6C 61 62 63 64 65 66 63 68 69 70 71 72 73 74 75 76 7;
G. Ii. HYDRIDE REDN. t
1. J. K. L. OXIDANTS
i- L L L L LLLLLLLLL HHHLLL L L L L L ML LLLLLL L L L L L LL
2 L L LL LLLLLLLLL HHHLHL L L L H L R L LLRLML L L LL L L R
3 RLML LLLLLLLLL HHMMML HHL M t M M LRRRRL HLLRM RR
6 L L LL LLLLLLLLL HHHHHL L L L H L R L LLRLLL MLL LL LH
8 BMML MLLLLLLML HHHLHM L R L H L RR LLRLML H LLL L LH

9 L L L L LLLLLLLLL HHHMHL L L L HLM L LLHLHL HL L L L LL

11 RL L L LLLLLLLLL HMMLHL H H L MLML LRRRRL HLLRM RR
12 L L L L LLLLLLMLL HHHLHL L L L H L ML LLRLHL H L CL L L R
13 RL L L LLLLLLMLL HHHLHL L L L HL ML LRRRRL HL L RM RR
15 L L L L LLLLLLHLL HHHMHL L LL H L ML LLRLHL HL LLL LR

16 RL L L LLLLLLLLL HMMLHL H H L ML ML LRRRRL HL L RM RR

17 L L L L LLLLLLLLL HHHLHL L L L ML RL LLRLHL HLLLL LM
10 L L LL LLLLLLMLL HHHMHM L L L H LM L LLLHRL R L L LL LH
21 RML L LLLLLLLLL HMMLML L L L RLR L RRRRRR RRLRM R R
22 L L L L LLLLLLLLL HHHLHL L LL ML L L LLLLLL L L LL L L L

23 HL L L LLRRLLLRL HHHLLL R L L RRR R RRRRRL MLLRL L R

26 H L L L LLLLLLLLL HHHLLL L L L R L R L LLLLLL L LLLL L L
28 RR L L RLLLLLLLL HLLLLL L L L RL RL LLLLLL L LLL L L L
3s HUH L LLLLLLMLL HHHLHH L L L HLL L LLLLHL H L LL L L L
36 HMLL LLLLLLMLL HHHLHH L L L H L L L LLLLHL HL LL L L L

37 HMLL LLLLLLMLL HHHLHH H L L L LLLMHL HL LL L L L

41 RR L R RRRLRRLRM HHHhfHL H L L L LLLLRL L L L L L L L
43 HLMH HHLHHHHHH HMMLHL HMRM LHLLHL HH L LH H H
4s L L LL LLLLLLMLL HLLLHM H L ML LLLLHL H L LLL L L
46 L L L L LLLLLLLLL HMMLHL HL ML LLLLLL L L L L L L L

40 L L L L LLLLLLLLL HLLLML L L M L LLLLLL 1HL LL L LL

Sl RRLL LLLLLLLLL HLLLHL RLRL LLLLLL IBL L L L LL
53 L L L L LLLLLLLLL HMMLHL HL ML L LLLL L, 1HL L L L L L
L
Reactivity Chart 1. Protection for the Hydroxyl Group: Ethers (Continued)

3 ‘3
s;
0
0”\2
o”o’o B
m
Fdx
2t!@Jv
+yE”----~~
PG 70 79 80 81 02 03 84 05 06 07 8E 89 90 91 32 93 94 BS 96 97 98 99 100 101-102 103 104 105 107
LO6 108
L. OXIDANTS n. N. 0. P.
1 L L H L LLLL LLL LLL L L L LLLLL L L L L L L L L L
2 L LB L Lx LL LHH LL R L LL LLLLL L L L M L L L L H
3 LL R L RHXL R RR LMR MRL HLLLL L L R R H R L L M
6 L LBl LLLLL LHH L L R L L L LLLLL L L L H L L L L H
8 LLPl LLH LL H H LL R LMR RLLLL M L L M

9 L L n L L B L L MHH L M H L L L LLLLL L L L H L L L L R
11 LL R LRHMM HH n n El HML MLLLL L L R R R R
12 LL R L LB LL HH LXE LLL LLLLL ML L M
13 LLR LRHHM R H LMH MML MLLLL M L R R R R
15 LL R LMHLL HH LMR L L L LLLLL H L L H

16 LL R L RHHH HH R RR MML MLLLL L L R R R R

17 LLM LCHLL WH LL R L LL LLLLL L L L H
L8 L LH LMHLL WH LM R L L L LLLLL H L L n
21 BL R Rf?RRL R R RR R n H M MLLLL L L R R
22 LL L L LLLL L LH LR R L L L LLLLL L L L L L L L L H

23 M RR L LRR L L RR LRR RR R MMLLL L L L M L L L L H

26 L L H tL L L L LLL L W R LL L LLLLL L L L M L L L L L
20 LLM L L L LL L LL Lkf R L L L LLLLL L L H M L L L L
35 LLL L LH L L LH L H R L LL LLLLL M L z" L L
36 L L L L LH LL LH LPIR LL L LLLLL L L L L

37 LL L LMHLL MH LM R L L L LLLLL ML L L
t1 LL L L L LLL L RR L LL MLLLL M L L L L
b3 L L L LHHLH kH"H L L R L L L LLLLM H L L H H L L L L
b5 L L L LWH LL HH L L R L LL LLLLL H L L M
t6 L L L L LHLL n L M L L R L L L LLLLL M L L M L L L L L

i8 LLL LLLLL LM L L R L LL LLLLL L L L L L

il L LH L LH LL MH L LR LLL LLLLL M L L L
i3 LL L L LHLL HH LLR LLL LLLLL M L L n
712 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

Reactivity Chart 2. Protection for Hydroxyl Group: Esters

1. Formate Ester
3. Acetate Ester
6. Trichloroacetate Ester
10. Phenoxyacetate Ester
19. Isobutyrate Ester
22. Pivaloate Ester
23. Adamantoate Ester
27. Benzoate Ester
3 1. 2,4,6-Trimethylbenzoate (Mesitoate) Ester
34. Methyl Carbonate
36. 2,2,2-Trichloroethyl Carbonate
39. Ally1 Carbonate
4 1. p-Nitrophenyl Carbonate
42. Benzyl Carbonate
46. p-Nitrobenzyl Carbonate
47. S-Benzyl Thiocarbonate
48. IV-Phenylcarbamate
5 1. Nitrate Ester
53. 2,4-Dinitrophenylsulfenate Ester

(See chart, pp. 713-715.)

Reactivity Chart 2. Protection for the Hydroxyl Group: Esters

PG 12 3 -4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38
A. AQUEOUS B. BASIC C. NUCLEOPHILIC D. ORGAWMET. E. CAT. REDN. F.
1 HHHMLLHHHH HLHHHHLH HHHHLM H HMMH MMM LL MML
3 HMLLLLMHHH RHHHHHLR HRMLLHL H HL LL LLLLL L L L
6 HMLLLLHHHH LHHHHLLL HRHHLR H HH H L RRRLR RRH
10 HMLLLLMHHH MMHHHHLR HRMHLL H H L LL LL L L L LL L
19 HMLLLLLMHH HHHHLMLH MMMLLL H H L LL L L L L L LLL

22 HMLLLLLLMH LLHMHLLM MMHLLLL H ML LL L L LL L L L L

23 HHLLLLLLMH LLHMLLLL LLLLLL L LLLL L LL L L LLL
27 HMLLLLLMHH LLHHLLLH MMMLLLL H H L LL L L LL L LLL
31 HMLLLLLLLH ~LHLHLLL LLLLLL L LLLL LLLLL L L L
34 HMLLLLLHHH LLHHHMLLH MMMLLLM RRL H M RLL LL RHH

36 HMLLLLMHHH L H HHH H L B RRMHLR RRLH M RLL LR H H H

39 HMLLLLLHHH LHHHMHLR MMMLLL RRL H L R RRL R LL L
41 HMLLLLHHHH LLHHRLLH RRMLLM RRM MM RRRLR RRR
42 HMLLLLLHHH LHHHMHLfl MMMLLLM RRL LL HHHLM LLL
46 HMLLLLLHHH LHHHRHLH RRMLLL RRLL L HHHLR RR R

47 HLLLLLLHHH LHHHRHLH RRMLLL R RMM H R RRL H LLL

48 HLLLLLLLMH RHHHRRLH MLMLLL RRL L L L LL L L L LL
51 HHMLLLLLHH LLHHHMLH HHHMLL H HMMM HHH LH H HH
53 HMMLLLLHHH LLHHHHLH HHHHHH MM HHH HHHLH HH H
-lA Reactivity Chart 2. Protection for the Hydroxyl Group: Esters (Continued)
P

.
PG 19 40 41 42 13 44 45 46 47 48 49 50 51 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77
G. H. HYDRIDE REDN. J. K. L. OXIDANTS
c
1 H L LL HHMMMMMHM L L L M LLL LLLLLL LH LLM HL
3 H L LL HMLLLLLHL LLL L L L L LLLLLL LLLLL LL
6 H H LL HHLLLMLHL L RL RLL L LLLLLL LHtLH HL
10 H H LL HMLLLLLHL L LL M LL L LLMLLL LL L L L ML
19 H H LL HLLLLLLHL L LL L LL L LLLLLL LLL LL LL

22 H L L L HLLLLLLLL LLLLLL L L L L LLL LLLLLL LL LL L LL

23 H L LL HLLLLLLLL LLLLLL L LL L LL L LLLLLL LL LLL LL
27 R L L L HLLLLLLHL LLLLML L LL L L L L LLLLLL L LL L L LL
31 H L LL HLLLLLLLL LLLLLL L L L LLRL LLLLLL L LLLL LL
34 H L LL HLLLLLLHL LLLLML L LL LLLL LLLLLL LH LL L LL

36 H R LL HMLLLLLHL RRLLML L R L M LL L LLLLLL LHLLM ML

39 H L LL HLHRLLLHL RRHLML M LL RRRR HHHHHL LRL R L H R
41 H H LL HMLLLMLHR RMLLML L L L L LL L LLLLLL LHLLM H L
42 H L LL HLLLLLLHL RRLLML L L L LLRL LLLLLL LL L L L LL
46 H R LL HLLLLLLHL RMLLML L L L LLRL LLLLLL LL LL L LL

47 H L LL HHLLMMLHM RMLLMt RM L L LL L LRRMRL RHL L L H R

48 H L LL HLMHLLLHL RLLLML L LL L LLL LLLLLL LL LL L LL
51 HHHM HHHHRHHHH RRRLML L L L H HH H LLLLLL MLLLL L L
53 HH H H HHHHHHHHH HHHLML MML R RRR LRRRRL RH LM H H H
Reactivity Chart 2. Protection for the Hydroxyl Group: Esters (Continued)

5
0 0 0‘
0 0 “0 cv u H
.N.
mk 2 s s 2 8 2
- ~~
PG 78 79 80 81 82 83 84 85 86 87 88 89 90 91 95 96 97 98 99 100 101 102 103 104 105 LO6 107 108
L. OXIDANTS M. 0. MISCELUINEOUS P.
.
1 LL L LLMMM L L LMH LLL LLLML L L L
3 LL L L L L L L L L L L M H L L L LLLLL L L L & R M L L L
6 LL L L L L L H L L MH H LL R RMLLL L L L
10 LL R LL LML LL L L H L L L LLLLL L L L
19 LL L L L L L L LL L MH L L L LLLLL L L L

22 LL L L L LL L L L L L MH L L L LLLLL L L L L L L L L L
23 LL L LL L L L L L L LH RL L LLLLL L L L
27 LL L L L LL L L L L L M H LL L LLLLL L L L L L L L L L
31 LL L L L L L L L L L MH LL L LLLLL L L L
34 LL L L L LL L L L L M H H LL L LLLLL L L L R L M L L L

36 LL L L L LL L L L L M H H L L H RMLLL L L L R R H L L L
39 MR R L L H H L L R M H H RRR HHLLL L L L
41 LL L LLLML L L M HH LL L RLLLL L L L
42 LL L LLMML L L L M H H L L L LLLLL L L L R M M L L L
46 LL L L L H H L L L M H H LL L HLLLL L L L

47 ML H L L LL L L R M HH L L L RLLLL L L L
48 LLL L L LLL L L M MH LL L LLLLR L L L R L
51 LL L L L LL L L L H H H LL L HLLHL L L L
53 ML R LMMML RR H H H L L M HMLML L L H
716 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

Reactivity Chart 3. Protection for 1,2- and 1,3=Diols

1. Methylenedioxy Derivative
2. Ethylidene Acetal
6. Acetonide Derivative
11. Benzylidene Acetal
13. p-Methoxybenzylidene Acetal
18. Methoxymethylene Acetal
20. Dimethoxymethylenedioxy Derivative
28. Cyclic Carbonates
29. Cyclic Boronates

(See chart, pp. 717-719.)

 S Hd '(11)x3
~YOH/uZ

xaddoaouo6q
xx~zouo6z~

xh
FTX
9 Hd 'N3I
ZT Hd ‘ND%

2 !-WC
,N3S !aEN !,a

+K(*HoT3)
.

HVN
~-
00Sf ‘ZT<Hd

ZT<Hd
U-01: Hd
OT-S'8 Hd
5’8-9 Hd
9-O Hd
P-t Hd
1: Hd
1 >Hd
0001 'T>Hd d

717
 SaN bl
OT Hd f3OQ
OOOf 'OSH
z"l
auotqrq
IT-Ol: Hd zoZt:
1 Hd 'for:
WfOX
004 'HE031
00 'HE03tl
0050 &E,
00 'L Hd 'pow

vos(
l w/T33c4
@lWSfU
l UI/xI

‘uy/al

r";d/(II)K

(II)6H
00 'HOwi
008 'HOW
JEI~W:~OTDTT
f38

oSZ ” TXQ
008 " TXQ
HTQf (WiO) F?

9-P Hd NSfH8EN
t(PHB)W
'HWN
00 "Hz8
H&rTHs,)
HBEng-T~
v HTQT?

S'H :fOSH
Ad/bS
(6H)TQ
f HN/QN

718
Reactivity Chart 3. Protection for 1,2- and 1,3=Diols (Continued)
-

+x u n
i3 8 E

PG -78 79 80 81 82 83 84 85 86 87 80 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 LO6 107 108
L. OXIDANTS M. N. 0. MISCELLANEOUS P.
1 L LL LLLLL L LL LLM LLL LLLLL M L L M L L
2 LLL LLMLL LM LLM LLL LLLLL M L L M
6 L L L LLMLL LMH L L L LLL LLLLL M L L M L L
11 LLR LL H LL LM LMH LLL LLLLL M L L M
12 LLR LLH LL LM LMH L M L LLLLL M L L R

18 LLL L M H L L L H LMH LL L LLLLM R L L R

20 LLL L M R L L L H MHH L L L LLLLM R L L R
28 L L L L LLLL L LL LMH L L L LLLLL L L L L L H L L L
29 LL L L H H L H H H H L HH L L L MLLMM H L L R L H L M H
720 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

Reactivity Chart 4. Protection for Phenols and Catechols

Phenols

1. Methyl Ether
2 . Methoxymethyl Ether
3 2-Methoxyethoxymethyl Ether
4: Methylthiomethyl Ether
6 . Phenacyl Ether
7 . Ally1 Ether
8. Cyclohexyl Ether
9 t-Butyl Ether
10: Benzyl Ether
11. o-Nitrobenzyl Ether
12. 9-Anthrylmethyl Ether
13. 4-Picolyl Ether
15. t-Butyldimethylsilyl Ether
16. Aryl Acetate
17. Aryl Pivaloate
18. Aryl Benzoate
19. Aryl9-Fluorenecarboxylate
20. Aryl Methyl Carbonate
2 1. Aryl2,2,2-Trichloroethyl Carbonate
22. Aryl Vinyl Carbonate
23. Aryl Benzyl Carbonate
25. Aryl Methanesulfonate

Catechols
27. Methylenedioxy Derivative
28. Acetonide Derivative
30. Diphenylmethylenedioxy Derivative
3 1. Cyclic Borates
32. Cyclic Carbonates

(See chart, pp. 721-723.)

Reactivity Chart 4. Protection for Phenols and Catechols

PG 19 20 21 22 23 24 25 26 27 28 29 30 51 32 33 34 35 16 37 30
c. NuCLEOPHfLIC 0. OEANOttET. E. CAT. REDN. P.
-
1 HMLLLLLLL L LLLLLLLL LLLHLHL L L L L L L L L L L L L L
2 HHHMLLLLL L LLLLLLLL LLLMLLL L L L L L LMLLL HML
3 HHLLLLLLL L LLLLLLLL LLLMLLL L LL L L LML LL LL L
4 HHMMLLLLL L LLRLLLLL LLLMLLL ML L L L RR R LR HHM
6 HLLLLLLLL H RRRRMRLR RRLMLML R RMMR MR RLL HIB H

7 HLLLLLLLM H LLRLRLLL RLLMLML R M L M L RR RL R ML L

0 HHLLLLLLL L LLLLLLLL LLLLLLL L L L L L LLLLL MLL
9 HHHLLLLLL L LLLLLLLL LLLLLLL L L L L L L L L LL HML
10 HHLLLLLLL L LLRLLLLL LLLMLLL M L L L L H HH LH L LL
11 HLLLLLLLL R LRRRLRLR LLLMLLL R RM R L HH H L B RRR

12 HMLLLLLLL L LLRLLLLL LLLHLML R M L L L H HH LH L L L

13 HLLLLLLLL L LLRLLLLL LLLMLLL R M L L L HH HLH ML L
15 HHHHNLLLM H LLLLLLLL LLLLLLL L L L L L L H L L L HMM
16 HHHMLLHHH H RRRHRRLH HHHMLHL R R L L L LM L L L L L L
17 HMLLLLLLM H LLRMLLLM MMLMLML L L L L L LL L L L LLL

18 HHHLLLLMH H LLRHLLLH MMMMLHL RR L L L L L L LL L LL

19 HMLLLLLMH H RRRRRRLH MMMMLHL R RL L L L L L LL LL L
20 HHHHLLLMH H LLRHMLLH MRMHLHM HH L L L LH L LL HHM
21 HMLLLLMHH H RRRRRRLH RRMMLHL H HM RM R L L L R HH H
22 HMLLLLLHH H LLRHLLLH MRMMLHL H H L L L R RR L R HL L

23 HHMLLLLMH H LLRHMLLH MMMMLHL H H L L L HHH LL MLL

25 LLLLLLLLH H RRRHLRLR MMMLLML HMLRM R L L L L L L L
27 HMLLLLLLL L LLLLLLLL LLLLLLL LML L L L L L LL L LL
20 HHHMLLLLL L LLLLLLLL LLLLLLL L LL L L LML LL HML
30 HHHHLLLLL L LLRLLLLL LLLLLLL L L L L L HHBLL H M M

31 HHHLLLLLH H RRHHRRLR HHHHLHM v HH HH L HLLL HHM

32 HHHLLLMHH H LLRHLLLH MMMLLHL R RL LL L L L LL MLL
- ~
Reactivity Chart 4. Protection for Phenols and Catechols (Continued)

l 8 s-4

i
da8

B RB tc

PG 39 40 41 42 I3 44 45 46 47 40 49 50 51 i2 53 54 5s 56 57 58 59 6( 61 62 63 64 i5 66 63 68 69 30 71 72 73 74 75 76 77
C. H. HYDRIDE REDN. L. J. K. L. OXID, ITS I
1 RL L L LLLLLLLLL HMLLLL L L L L L L L LLLLLL T-r
2 RL L L LLLLLLLLL HHHMHL L L L H L R L LLLLML RL L L L L L
3 R L L L LLLLLLLLL HMLLHL L L L ML R L LLLLLL ML L L L L L
4 R L L L LLLLLLLML HHMLML H ML H L R L LRRRRL R L L RL RR
6 RR L L RRRRRRRRR HHLLML L L L L L L L LLLLRL L L LLL LL

7 RL L L LLRRLLLLL HHLLLL R L L R RR R RRRRRL L L LRL L R

0 R L L L LLLLLLLLL MLLLLL L L L ML L L LLLLLL L L L L L LL
9 R L L L LLLLLLLLL HHHLHL L L L ML L L LLLLLL R L L L L LL
10 RL L L LLLLLLLLL HMLLLL L L L RR R R LLLLML L L LL L L L
11 RR L L RRLLLLLRL HMLLLL L L L M M M M LLLLML L L L L L L L

12 RL L L LLLLLLLLL HMLLML L L L R RR R LLLLML L L L L L LL

13 RL L L LLLLLLLLL HHLLML L L L RR RR LRRRRL H L L L L L L
15 R L L L LLLLLLMML HMLLHL L L L H L L L LLLLML R L LL L L L
16 R L L L HHLLMLLHM RRMLHL L L L L L L L LLLLLL L H L L L HL
17 RL L L HLLLLLLML RLL LML L L L L L L L LLLLLL L L LL L L L

18 R L L L HMLLLLLHM RRMLHL L L L L L L L LLLLLL L H L L L HL

19 RL L L HHLLLLLHM HHLLHL L L L R L R L LLLLLL LM L L L HL
20 R L L L HLLLLLMHM HHLLHM L L L H L L L LLLLLL HMLL L ML
21 RML L HMLLMLLHM HHLLHL L R L ML L L LLLLLL L R LL L RL
22 R L L L HLRRLLLHM HHLLHL H L L RR R R RRRRRL RR LRL RR

23 R L L L HLLLLLLHM HHLLHL L L L ML R L LLLLML MML LL L L

25 R L L L LLLLLLLLL HLLLLL L L L L L L L LLLLLL LL L LL L L
27 R L L L LLLLLLLLL HH LLM L L L L M L R L LLLLLL M L L L L L L
28 R L L L LLLLLLMLL HHMLML L L L H L L L LLLLLL RL LLL L L
30 RM L L LLLLLLLLL HHM LML L L L H L L L LLLLLL RL LL L L L

31 RM L L HHHHHHHHH HHHLHL L L L H L L L LLLLRL RL L L L L L

32 R L L L HLLLLLLHM HHLLHL L L I H L L L LLLLLL R RLL L ML
1
Reactivity Chart 4. Protection for Phenols and Catechols (Continued)

33
s;
cue
0” \(Y
c%82 );:
ig
70 79 00 01 02 03 04 05 06 07 08 09 90 91 92 93 94 B5 96 97 90 99 100 101 102 103 104 105 106 107 100
L . OXIDANTS n. N. 0. uI0cEm P.
t
1 L L L L L L L L L L L L L L L L L LLLLL L L L L L L L L L
2 L L L L L M L L M R R L M Ii L L L LLLLL L L L L L L L L H
3 L L L L L L L L L L L L M H L L L LLLLL L L L L L L L L L
4 L L R L R M L L R R R L M H M R L MLLLL L L R R L L L L M
6 L M M L L R L L M R R L L M R R L LLLLL L L L M R M L L L

7 L R R L L H M L L R R M R R R R R MMLLL L L L M L L L L R
0 L L L L L L L L L L L L L L L L L LLLLL L L L L L L L L L
9 L L L L L L L L L M L L M H L L L LLLLL L L L L L L L H
10 L L L L L L L L L L L L L L L L L LLLLL L L L” L L L L L L
11 L L L L L L L L L L L L L L L L L LLLLL L L L L L L L L L

12 L L M L L L L L L L L L L L L L L LLLLL L L L L L L L L L
13 L L L L L L L L L L L L L L L L L LLLLL L L R R L L L L L
1s L L L L L M L L M R R L L L L L L LLLLL M L L L L L L L L
16 L L L L L M L R L L H L L L L L L LLLLL L L L L R H L L L
17 L L L L L L L L L L L L L H L L L LLLLL L L L L L L L L L

18 L L L L L L L L L L L L L n L L L LLLLL L L L L L M L L L
19 L L L L L L L L L L L L L M L L L LLLLL L L L R M L L L
20 L L L L L ii L L L M R L M H L L L LLLLL L L L” R L M L L M
21 L L L L L L L M L L L L M H L L R RMLLL L L L M R H L L L
22 M R R L L L L L M R R L M H R R R RRLLL L L L R L H L L R

23 L L L L L L L L L L R L M H L L L LLLLL L L L R L M L L L
2s L L L L L L L L L L L L L n L L L LLLLL L L L L R L L L L
27 L L L L L L L L L L L L L L L L L LLLML L L L L L L L L L
28 L L L L L M L L L M H L L H L L L LLLLL L L L L L L L L M
30 L L L L L R L L L R R L M H L L L LLLLL L L L L L L L L n

31 L L L L L L L L L R R L M H L L L LLLRR R L R R R R R R H
32 L L L L L L L M L L M L L M L L L LLLLL L L L R L L L L L
724 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

Reactivity Chart 5. Protection for the Carbonyl Group

1. Dimethyl Acetals and Ketals

3. Bis(2,2,2-trichloroethyl) Acetals and Ketals
5. 1,3-Dioxanes
6. 5Methylene- 1,3-dioxanes
7. 5,5Dibromo- 1,3-dioxanes
8. 1,3-Dioxolanes
9. 4-Bromomethyl- 1,3-dioxolanes
10. 4-o-Nitrophenyl- 1,3-dioxolanes
11. S,S’-Dimethyl Acetals and Ketals
19. 1,3-Dithianes
20. 1,3-Dithiolanes
24. 1,3-Oxathiolanes
26. O-Trimethylsilyl Cyanohydrins
29. IV&V-Dimethylhydrazones
30. 2,4-Dinitrophenylhydrazones
33. O-Phenylthiomethyl Oximes
34. Substituted Methylene Derivatives
43. Bismethylenedioxy Derivatives

(See chart, pp. 725-727.)

Reactivity Chart 5. Protection for the Carbonyl Group
I
s ii rp
m I‘-
m’x vi x
Q, 2(d ii z ‘- z’ a
PfipiJg
PG i2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 31 32 33 34 35 36 37 38
A. AQUEOUS B. BASIC C. NUCLEOPHILIC E. CAT. REDN. F.
1 HHHLLLLLLL LLLLLLLL LLLLLL L L L LL L L L L L HH L
3 HHHLLLLLMR RRHRRRLR RRMRRR R RR RR RRRLM H RM
5 HHHLLLLLLL LLLLLLLL LLLLLL LLL L L LML L L H HM
6 HHHLLLLLLR LLHRRLLL LLLLLL L LL LL RR RL R H HM
7 HHHLLLLMRR RRHRRRLR RRMRRR RRR RR RRRLM H RM

8 HHHMLLLLLL LLLLLLLL LLLLLL L L L L L L R L L L HL L

9 HHHMLLLLRR RRHRRRLR RRLRRR LRRML R RR LL H H M
10 HHHMLLLLLH LMHHLRLM LMLLLL RRMRL RRRMR H RR
11 RRLLLLLLLL LLLLLLLL LLLLLL L LL L L R RR HR L L L
19 RMLLLLLLLL LLLLLLLL LLLLLL L L L L L RRRHR L L L

20 RRLLLLLLLH LLLLLLLL LLLLLL L L L L L RRLHR LLL

24 HHHHLLLLLR LLLLLLLL LLLLLL L L LLL RRRHR HM L
26 HHHHHHHHHH LLRRMLLR HLLHLL MMH LR RR RLR H RR
29 HLLLLLLLLH LLMLLRLL LLRLLL L LLLL RRR LR H HM
30 HLLLLLLLLH RRRRRRLR MMLLLL RRR LR RRRLR R R R

33 HHMLLLLLLR LRHLLMLL LLLLLL R LL L L RRR LR R RM

34 RMLLLLLLHH HHRRRRLR HRMLLL R RRR R RRLLR M M M
43 HHMMLLLLLL LLLLLLLL LLLLLL L L L LL L LL LL H H L
Reactivity Chart 5. Protection for the Carbonyl Group (Continued)

PG 39 40 41 42 13 44 45 46 47 48 49 50 51 52 53 54 5556 57 58 59 63 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77
G. H. HYDRIDE REDN. I. J. K. L. OXID NTS
1 L L L L LLLMLLLLL H R H L-H M L L L H LL L LLLLLL H L L L L L L
3 RM L L RLLMLLLLL HHHLHM L R L RRRR LLLLLL H L L L H L L
5 L L L L LLLMLLLLL HHHLLL L L L H L L L LLLLLL M L L L L L L
6 RL L L LLRRLLLLL HHHLHM R LL H R H R RRRRRL H L L M L L R
7 R H M L RLLLLLLMM HHHLLt L RL H H H H LLLLLL H L L L H L L

8 L L L L LLLMLLLLL HHHLLL L L L H LL L LLLLLL H L L L L L L

9 LH L L MLLMLLLLL HHHLLL L RL H H L L LLLLLL L L L L R L L
10 RRL L RRLMLLLLL HHHLLL LL L H H L L LLLLLL H L L L L L L
11 R L L L LLLLLLLLL HLLLLL H H H H L L L LRRRRL M L L R M R R
19 R L L L LLLLLLLLL HLLLLL H H H H L L L LRRRRL M L L R M R R

20 R L L L LLLLLLLLL HLLLLL H H H H L L L LRRRRL M L L R M R R

24 RL L L LLLLLLLLL HHMLHL H H H H L L L LRRRRL H L L R M R R
26 RR M L RRRRMMLRR HHHMHH L L L R L H L LRHRRL RR LL R R R
29 tL R L RLLRLLRRL HLLLLL LLR R M L M LHHHHH H H L H L H H
30 RR M L RRLLLMRRM LLLLLL L L H RL L L LLHHHL L L L M L H R

33 RRM L LLLRLLRRM HMLLLL R RM RLR L LRHRRL R L L R M M R

34 RR M L RRRRMLRRM MLLLLL L L L R RR R RRHRRL M L L M M M M
43 L L L L LLLLLLLLL RRMMLL L L L M LL L LLLLLL L L L L L L L
--
?eactivity Chart 5. Protection for the Carbonyl Group (Continued)

e, ‘3
c:
2 c: ;;:
0” c d 3
H” 0
n 8
zou ki OJ 0
u l o z” 8 x 8 P k! t‘
.p
78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94
95 96 97 98 99 100 101-102 103 104 105 . LO6 107 108
M. N. 0. MISCELLANEOUS P.
L. OXIDANTS
1 LLL L L M L L L L L L H H LLL LLLLL L L L M L & M
3 L L L L L M L L L L L M R L #d H RMLLL L L L M L L M
5 L L R L L M L L L L L L R L L L LLLLL L L L L L L L
6 R R R LRMRL R R L L R R R R LRLLL L L L M L L R
; 7 L L R L L M L L L L L L R L M H RMLLL L L L M L L M

8 L L R L L H L L L L L L R L L L LLLLL L L L L L L R
9 L L R L M H L L L L L L R L L H RLLLL L L L M L L M
10 L L R L M H L L L M L L R L L L RLLLL L L L M L L M
11 ii L R M R M L L R R L L R M M L MLLLL L L R R L L M
19 LLR M R M L L L M L L R M M L MLLLL L L H L L & M

20 H L R MRM LL RR L L R M M L MLLLL L L H R L L L
24 L L R L R M L L R R LL R M M L MLLLL M L R R L L M
26 L L R R R R L R R R LMR L R L LLLLR R L L M L I, R
29 L L H M H L M L R R L R R R R R LLLLL L L R R L L M
30 L L L M H L L L R R L M R R R R LLLLL L L M R L L L

L L R LRMLL R R L R R R R R MLLLL L L R R L L M
L L R R L L L L L L L M R R R R RLLLL L L L M L L R
L L L L L L L L LM L L L L L L LLLLL M L L M L L L
728 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

Reactivity Chart 6. Protection for the Carboxyl Group

Esters

1. Methyl Ester
2. Methoxymethyl Ester
3. Methylthiomethyl Ester
4. Tetrahydropyranyl Ester
7. Benzyloxymethyl Ester
8. Phenacyl Ester
13. IV-Phthalimidomethyl Ester
15. 2,2,2-Trichloroethyl Ester
16. 2-Haloethyl Ester
2 1. 2-( p-Toluenesulfonyl)ethyl Ester
23. t-Butyl Ester
27. Cinnamyl Ester
30. Benzyl Ester
3 1. Triphenylmethyl Ester
33. Bis(o-nitrophenyl)methyl Ester
34. 9-Anthrylmethyl Ester
35. 2-(9,10-Dioxo)anthrylmethyl Ester
42. Piperonyl Ester
45. Trimethylsilyl Ester
47. t-Butyldimethylsilyl Ester
50. S-t-Butyl Ester
59. 2-Alkyl- 1,3-oxazolines

Amides and Hydrazides

64. NJV-Dimethylamide
68. N-7-Nitroindoylamide
7 1. Hydrazides
72. IV-Phenylhydrazide
73. NJ/‘-Diisopropylhydrazide

(See chart, pp. 729-731.)

Reactivity Chart 6. Protection for the Carboxyl Group
I
+ + :
$:
N l - 9

*Iii! f! N I .2 8 *
2 z c3’% “a x

5 5 z a 8 8 ij
.:I 0) a
g 28
x xmIii I cr N ‘- z‘ aE 2
x c*l s:w8 :I 4 z l - is {&xp$ fPPS
2 E” y ‘A 2 g
s! E 0 0 -2
PC 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 2: 26 27 28 29 30 31 32 33 34 35 36 37 38
A. AQUEOUS B. BASIC C. NUCLEOPHILIC D. ORGANOMET. E. CAT. REDN. F.
-i HHLLLLLMHH LLRRLLLL LRMHLL R R L L L L L L L L L L L
2 HHHMLLLLHH LLRRLLLL RRMLLL R R L L L L L L LL H M L
3 HMLLLLLLMH LLRRLLLL RRMMLL RRLL L RR R LR H M M
4 HHflHLLLMHH LLRRLLLL RRMLLL R R L L L L H L L L H H L
7 HHHMLLLLHH LLRRLLLL RRMLLL RR L L L H H H LM H M L

0 HLLLLLLMHH RRRRMRLR RRMHLH RR R L R H H H LM H H H

13 HHLLLLHHHH LLRRLLLL RRHLLL RR L L L L ML LM H R L
15 RL&LLLMHHH RRRRRLLR LRMMLM R RM R& RRLLL H H M
16 HHMLLLLHHH RRRRRRRR RRMRLH RR R R R R RR L L M M M
21 HHLLLLMHHH RRRRRRRR RRMRMH RR L L H R LL LL M M M

23 HHHHLLLLHH LLRRLLLL LLLLLH RRLLL L L L L L H t L

27 HHHLLLLHHH LLRRLLLL RRMLLL RR L H L R RR LR ML L
30 HMLLLLLHHH LLRRLLLL RRMMLL RR L L L HHHLL L L L
31 HHHHMLLMHH LLRRLLLL RRLLLL RR LL L H H H LM H H M
33 HMLLLLLMHH LLRRLLLL RRMLLL R RL L L RR R L R RR R

34 HHMLLLLLHH LLRRLLLL RRMHLL RR L L L H H H LM ML L

35 HHLLLLLMHH LLRRLLLL RRMMLL RRM L M H H H L M RR L
42 HHHLLLLMHH LLRRLLLL RRMMLL RRL L L H H H LM H M L
45 HHHHHHHHHH LLRRLLLL RRHHHH RRH H H H H H H H H H H
47 HHHHHMHHHH LLRRLLLL RRMLLL RR L L L L H L LL H H H

50 HHMLLLLLMH LLRRLLLL RRRRMH RR R RL RR RL R H L L

59 HI! M L LL L L bf H L Lit L L L L L LLLRLL L L L L L RR R LR RRR
64 HLLLLLLLLH LLMMLLLL LLLLLL R R L L L ML L LL L L L
68 HMLLLLLMHH LLRHHLLL LMLLLL RR LL L RR R R R R RR
71 HHMLLLLLMH RRRRRRLR RLLLLL RR LL L H H M L L MLL

72 HHMLLLLLMH RRRRLRLR RLLLLL R R L L L HHMLL ML L

73 HHLLLLLLLH LLHRLRLR LLLLLL RR L L L H H M L L ML L
- --
730
Reactivity Chart 6. Protection for the Carboxyl Group (Continued)

3 -
2
$g
cuu
;f 8 ;
2 2 E i!
78 79 80 81 82 83 84 85 86 07 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108
L. OXIDANTS M. N. O.MISCELLANEOUS P.
L L L L L L L L L L L L L L L L LLLLL L L L L L L L
LL R LLLLL LH L L R L L L LLLLL L L L L L n
LL R LRMLL RR L L R M M L MLLLL L L R" R L L L
LLB¶ L LH LL LH MRR L L L LLLb'M M L L L L L n
LLR LLMLL L H L L R L L L LLLLL M L L L L L n

0 LRR LLLL L L L L L R L L L LLLLL L L L L L L L

13 LL L L L LL H L L L M R L L L LLLLL L L L R L L L
15 LLL L L L LM L L M A I? L M R RMLLL L L L L L L L
16 LLL LLLLL L L L M R L L R RLLLL L L L L L L L
21 LL L L LLL L L M M H R L L L LLLLL L L L L L L L

23 L L L L L ii L L L H MHH L L L LLLLL M L L L L L H
27 R R R L L M L L L M R R I? RR R LRLLL L L L L L L R
30 L L L L L M L L L L L L R L L L LLLLL L L L L L L L
31 L L L L L H L L L H M H R L L L LLLLL M L L L L L H
33 L L L L L L L L L L L L R L L L LLLLL L L L L L L L

34 L L L L L M L L L L L L R L L L LLLLL L L L L L L L
35 L L M L L M L L L L L L R L L L LLLLL L L L L L L L
42 L L M L L M L L L R L L R L M L LLLLL L L L L L L R
45 Ii L L L H H L H H H L L R L M L LLLLH H L L H L M L
47 H L L L M H L H H H L L R L L L LLLLL H L L L L M L

50 L L R L LL LL L R M H R M M L LLLLL L L L R L
59 L L R L LMML L R L L R L L L LLLLL L L R R L" i R
64 L L L LL LL L L L L L L L L L LLLLL L L L R L L L
68 L L M L L L L L L M L L M R R R LLMLL L L L R M
R R R RRRMR 8 R M R R L R L LLLRR R L R R R” R” R
71

72 H R R H H R M H M R R L M L LLLRR R L R R R R R
H R R H R R M H M R R L M L LLLRR R L R R R R R
73
BP-
732 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

Reactivity Chart 7. Protection for theThiol Group

1. S-Benzyl Thioether
3. S-p-Methoxybenzyl Thioether
5. S-p-Nitrobenzyl Thioether
6. S-4-Picolyl Thioether
7. S-2-Picolyl IV-Oxide Thioether
8. S-9-Anthrylmethyl Thioether
9. S-Diphenylmethyl Thioether
10. S-Di( p-methoxyphenyl)methyl Thioether
12. S-Triphenylmethyl Thioether
15. S-2,4-Dinitrophenyl Thioether
16. S-t-Butyl Thioether
19. S-Isobutoxymethyl Monothioacetal
20. S-2-Tetrahydropyranyl Monothioacetal
23. S- Acetamidomethyl Aminothioacetal
25. S-Cyanomethyl Thioether
26. S-2-Nitro- 1-phenylethyl Thioether
27. S-2,2-Bis(carboethoxy)ethyl Thioether
30. S-Benzoyl Derivative
36. S-(IV-Ethylcarbamate)
38. S-Ethyl Disulfide

(See chart, pp. 733-735.)

Reactivity Chart 7. Protection for the Thiol Group
I
E
m $f
04 l- a
I
m’x % x
z B z c4
0) d
l- z‘
b
sgytJtJg
..
x ti x x x x x x -x 3=
aaaaaaacr(a a 2
2 3 h ~5~~~678---g~o
E- 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38
A. AQUEOUS B. BASIC C. NUCLEOPHILIC D.ORGANOMET. E. CAT. FtEDN. F.
1 HLLLLLLLL M LRRRLRLL LLLLLL R RL LL RRRMR L LL
3 HHMLLLLLL M LRRRLRLL LLLLLL R RL L L RRRMR MLL
5 HLLLLLLLM H MRRRLRLR MLLMLM R RL RL RRRMR RRR
6 HLLLLLLLL M LRRRLRLL LLLLLL RRL L L RRRMR L L L
7 HHMLLLLLL M LRRRLRLL LLLLLL R RL L L RRR R R R RR

8 HMLLLLLLL M LRRRLRLL LLLHLL R RL LL RRRMR LLL

9 HLLLLLLLL M LRRRLRLM LLLMLL R RL L L RRRMR LL L
10 HHLLLLLLL M LRRRLRLM LLLMLL RRL LL RRRMR L L L
12 HHMLLLLLL M LLRLLLLL LLLRLL LLL LL RRR R R ML L
15 HLLLLMHHH H RRRRRRLR MMMHLH RRL RL RRRRR RRR

16 HMLLLLLLL M LLLLLLLL LLLLLL L LL L L RRM LM LLL

19 HHLLLLLLM H LLRHLLLL LLLHLL L LL LL RRRL R HL L
20 HHLLLLLLM H LLRHLLLL LLLRLL LLLLL RR RL R HLL
23 HMLLLLLLL H RRRRLRLR RLLLLL R RL L L RRRMR L L L
25 HRLLLLLMM H RRRRMRLR RLLLLL RR L LL RRRL R RRL

26 HLLLLLHHH R HHRHHHHH HRHMLM RRL RL RRR R R RR R

27 HLLLLLLHH R HHRHHHLH RRRMLM RRRRL RRRL R LL L
30 HLLLLLMHH H LLHHHHHH HHHHLH H HH LH RRRLR HL L
36 HLLLLMHHH H RRRHHRHH HHHHLL HHL L L RRRLR HL L
38 HLLLLLLLH H RRRHRRLR RRLMLH HH HMH RRRH R HH H
--
3 Reactivity Chart 7. Protection for the Thiol Group (Continued)

0
0
0 0 8
0 rl

. v)
% 0‘ P
X* 0
2 k? B ir
--~
PG 39 40 41
42 13 44 45 46 47 48 49 50 51 52 53 54 5556 57 58 59 6C 61 62 63 64 65 66 67 68 69 70 71 72 33 74 75 76 77
G. H. HYDRIDE REDN. I. NY. K. L. OXIDANTS
i- ljlL L
L LLLLLLLLL L L L L-M L -L M L R L R R LRRRRL RL L R L RR
3 IjlL L
L LLLLLLLLL MLLLML R RL R L R R LRRRRL RL L R L RR
5 HRL L RMLLLLLLL LLLLML LLL R L R R LRMRRL RLLRL RR
6 HLL L LLLLLLLLL MLLLML LL L R L R R LRRRRL RLLMM RR
7 H R RR RRLRMLLRR HMLLLL LL L R L R R LRRRRL RLLML RR

8 HL L L LLLLLLLLL MLLLML MML R L R R LRRRRL RL L R L RR

9 HL L L LLLLLLLLL HMLLML MML R L R R LRRRRL RL L R L RR
10 IYL L L LLLLLLLLL HMMLML R RL R L R R LRRRRL RL L R L RR
12 IYL L L LLLHLLLLL HHMLML RRL L L L L LRRRRL RL LML RR
15 R RM L RMMMLLLRL LLLLML L LL L L L L LRLMRL RRLMR RR

16 LL L L LLLLLLLLL HMLLML R R L L L L L LRRRRL RLLML RR

19 HL L L LLLLLLLLL HHMLML R R L L L R L LRRRRM RL LML RR
20 ML L L LLLLLLLLL HHMLML R R L L L R L LRRRRM RL LML RR
23 L L L L RLRRLLLRL LLLLML R R L L L L L LRRRRL RLLRL RR
25 RL L L RMLRLLLRL MLLLML L L L R L R L LRRRRL RR L R L RR

26 RRL L RMLLLLLLR L L L LM L L L L RLR R LRRRRL RR L RM RR

27 RL LL RRLLLLLRL M L L LM L LLL L LR L LRRRRL RRLML RR
30 HL LL HHLMHMLHL RMLLML RRL L LML LRMRRL RHL R L RR
36 HL L L HMMHLLLHL RHLLML R RL L LM L LRRRRL R E L R M RR
38 HH H H HHHHHHMHH RHLLML RRM RRRR MRRRRR RL RRL RR
Reactivity Chart 7. Protection for the Thiol Group (Continued)

n
i
e, ‘3 0 4
. $ et 3 m
ONe 8
E 2 8 2 u H XW
Fi
$m 3!
z i! 8.. %
z 8cy x
PG 78 79 80 81 82 83 84 85 86 87 8t 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 LO6 107 108
L. OXIDANTS M. N. 0. MISCELLANEOUS B.
i- L LR MRRML RR LLM MRL RLLLL L, L R R R R L L M
3 ML R MRRML RR L LM MRL RLLLL L L R R R R L L M
5 RL R LRRLL RR L LM MRL RLLLL L L M M R M L L L
6 RL R LRRML RR L LM MRL RLLLL L L R R R R L L L
7 RL R LRRML RR L LM RRL RLLRR R L R R R R L H L

8 RL R MRRRL RR LLM MRL RLLLL L L R R R R L L M

9 ML R MRRRL RR L LM MRL RLLLL L L R R R R L L M
10 ML R MRRRL RR L LM MRL RLLLL L L R R R R L L M
12 R L M L RLL L RR L LM MRL LLLLL L L L L L L L L M
15 RL M LLML R RR LLM MRL RLLLL L L L L R L L L L

16 L LM L RLL L RR L LR MRL LLLLL L L M M M M L L M

19 RL R L RML L RR LMR MRL MLLLL L L R R M R L L M
20 RL R L RML L RR LMR M RL MLLLL L L R R M R L L H
23 R L R L RML L RR LLM MRL LLLLL M L R R R R L L L
25 RL R L RMLM RR LLM M RL MLLLL L L R R R R L L L

26 RL R LRMLH RR MHH MRL RLLLL L L R R R R L L L

27 RL R L RML H RR MHH MRL LLLLL L L R R R R L L L
30 LL R L L LL H LM M RR MML LLLLL L L L R L L L L L
36 LL R L RLLH LM RRR MML RLLLL M L L R L L L L L
38 RL R RRRRR RR H HR MRR RRLLL L L M R R M L L R
 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

Reactivity Chart 8. Protection for the Amino Group:

Carbamates
1. Methyl Carbamate
5. 9-Fluorenylmethyl Carbamate
8. 2,2,2-Trichloroethyl Carbamate
11. 2-Trimethylsilylethyl Carbamate
16. 1,l -Dimethylpropynyl Carbamate
20. 1-Methyl- 1-phenylethyl Carbamate
22. 1-Methyl- 1-(4-biphenylyl)ethyl Carbamate
24. 1,l -Dimethyl-2-haloethyl Carbamate
26. 1,l -Dimethyl-2-cyanoethyl Carbamate
28. t-Butyl Carbamate
30. Cyclobutyl Carbamate
3 1. 1-Methylcyclobutyl Carbamate
35. 1-Adamantyl Carbamate
37. Vinyl Carbamate
3 8. Ally1 Carbamate
39. Cinnamyl Carbamate
44. 8-Quinolyl Carbamate
45. WHydroxypiperidinyl Carbamate
47. 4,5-Diphenyl-3-oxazolin-2-one
48. Benzyl Carbamate
53. p-Nitrobenzyl Carbamate
55. 3,4-Dimethoxy-6-nitrobenzyl Carbamate
58. 2,4-Dichlorobenzyl Carbamate
65. 5-Benzisoxazolylmethyl Carbamate
66. 9-Anthrylmethyl Carbamate
67. Diphenylmethyl Carbamate
7 1. Isonicotinyl Carbamate
72. S-Benzyl Carbamate
75. N-(WPhenylaminothiocarbonyl) Derivative

(See chart, pp. 737-739.)

Reactivity Chart 8. Protection for the Amino Group: Carbamates

19
PG 12 3 4 5 6 7 8 9 10 20 21 22 23 24 25 26 27 28 29 30 11 32 33 34 35 16 37 38
A. AQUEOUS C. NUCLEOPHILIC D. ORGANWET. E. CAT. REDN. F.
-i HHLLLLLLM H LLLLLLLL LLLHLLL H L L L L L L L L L L L L
5 HMLLLLLLM H MHLLLLMH MLHLLML H H ML L LLMLR L LL
8 HHLLLLLLM M RRRRRRLR LRMMLLL H H R R R L L L L L H H H
11 HHHMLLLLL M LLLLLLLL LLLLLLL H H L L L LM L L L ML L
16 HHHLLLLLL M LRRRLRLR LLLLLLL H H RM R H H HH R H H L

20 HHMLLLLLL M LLLLLLLL LLLLLLL H H L L L MH L L R H H L

22 HHHMLLLLL M LLLLLLLL LLLLLLL H H L L L MH L L R H H H
24 HHMLLLLLL H LLHLLLLM RRMLLLL H H M RM M R R L L H HH
26 HLLLLLMHH H MRMHHHHH HHHHMHL H H H M M R RR L R R R L
28 HHMMLLLLL M LLLLLLLL LLLLLLL H H L L L L H L L L H HM

30 HHMLLLLLL H LLLLLLLL LLLLLLL H H L L L L ML L L H ML

31 HHHMLLLLL H LLLLLLLL LLLLLLL H H L L L LM L L L H ML
35 HHHMLLLLL M LLLLLLLL LLLLLLL H H L L L L ML L L H H L
37 HHHHMLLLL M LLLLLLLL LLLLLLL H H L L L H HH L R H HM
38 HHMMLLLLL M LLLLLLLL LLHLLLL H H L L L H H H L R H H L

39 HHMMLLLLL M LLLLLLLL LLHLLLL H H L L L H H H L R H H L

44 HHMLLLLLH H LLLLLLLL LLLLLLL H H L L L L L L L L H H L
45 HLLLLLLLL M LLMLLLLL LLLLLLL H H L L L L H H L H H H L
47 HLLLLLLLL M LLHLLLLL MMLLLLL H H L L L R H H L R L L L
48 HHLLLLLLL H LRLLLLLH LLHLLLL H H L L L H HH L R M L L

53 HHLLLLLLL M LRRLLLHH MMHLLLL H H L R L H H H L R RR R

55 HMLLLLLLL M LLLLLLLL MMMLLLL H H L R L H H H L R RR R
58 HMLLLLLLL M LLLLLLHM MMHLLLL H H M L L H H H L R L L L
65 HHMLLLLLM H LRHHHHRH HHHHLML H H L L L H H H L R HM L
66 HHLLLLLLL M LRLLLLLL LLLHLLL H H L L L H H H L R MML

67 HHHMLLLLL M LRLLLLLL LLHLLLL H HM L L H H H L R HML

71 HLLLLLLLL M LRLLLLLL LLMLLLL h H L L L H HH L R HHL
72 HHLLLLLLH H LRHLLLLL HMHLLML HH L L L H R H L R L L L
75 HHMLLLLLH H LLLLLLLL LLLLLLL HHML L RR R L R HH R
Reactivity Chart 8. Protection for the Amino Group: Carbamates (Continued)

39 40 41 42 b3 44 45 46 47 40 49 50 51 52 53 54 5556 57 58 59 60 61 62 63 64 55 66 67 68 69 70 71 72 73 74 75 76 77
G. H. HYDRIDE FtEDN. I. J. K. L. OXIDANTS
1 L L L L RLLLLLLRL RLLLLL L L L L L L L LLLLLL H L L L L t
5 H L L L MLLLLLLML R L L LM L L L H R R R L LLLLLH L L L L L L L
8 R M H L RLLLLLLML R R R LL L L L L M M M M LLLLLL L L L L R L L
11 L L L L RLLLLLLML R L L LB H L L L L L L L LLLLLL H L L L L L L
16 H L L L RLRRLLLML R H L LR H R L R R R L R RRRMRL H L L L L L R

20 R L L L RLLLLLLML R H M LR H L L L L L L L LLLLLL H L L L L L L
22 R L L L RLLLLLMML RHMLRH L L L H L L L LLLLML H L L L L L L
26 H L H L RLLLLLLML RHMLML L M L M L L L LLLLLL M L L L R L L
26 H L L L RMLMLLLML R H M LM L L L H L L L L LLLLLH L R L L M M L
28 L L L L MLLLLLMLL R H M LR H L L L H L L L LLLLML H L L L L L L

30 L L L L MLLLLLLML R M L LM L L L L M L L L LLLLLL M L L L L L L
31 L L L L HLLLLLLML R M M LR M L L L M L L L LLLLLL H L t L L L L
35 L L L L MLLLLLLML R L L LL L L L L M L L L LLLLLL H L L L L L L
37 L L L L RLRRLLMML R L L LR L R L L R R R R RRRRRL H L L R L L R
38 L L L L RLRRLLLML R H H LR L R L L R R R R RRRRRL M L L M L L R

39 H L L L RLRRLLLML R H H LR L R L L R R R R RRRRRL M L L R L L R
44 H L L L MLLLLLLML R L L LL L L M H R L L L LLLRRL L L L L L L L
65 H L M L MLLLLLLML R L L LL L L L L L L L L LLLRRL L L L L L L L
47 H L L L MLMRLLLML RLL LML L L L R R R R MMMHHL M L L R L L R
68 H L L L RLLLLLLLL RLLLRL L L H H R R L LLLLLL L L L L L L L

53 H R L L RLLLLLLML R L L LL L L L H M L R L LLLLLH L L L L L R L
55 H R L L RLLLLLLML R R L LR L L L L M L R L LLLLLL L L L L L M L
58 H L L L RLLLLLLML R H L LM L L L H M L R L LLLLLH L L L L L L L
55 H L M L MLLLLLLML R H L LR L L L H H R R L RRRRRR M L L M L L R
id H L L L MLLLLLLML R H L LR L L L L R R R R LLLLLL L L L R L L L

i7 H L L L HLLLLLLML R H L LR L L L L H R R L LLLLML H L L L L L L
‘1 H L L L MLLLLLLML R M L LR L L L L M M R L LLLRRL L L L L L L L
'2 BLML MLLLLLLML RHLLRL H H L R R R L LRRHHL LMLLL R R
'5 BBLL MLLLLLLML RHMLLL R H M R R R L LLRHBL MHLRR RR
Reactivity Chart 8. Protection for the Amino Group: Carbamates (Continued)
I

FG 78 79 80 81 82 03 84 05 86 07 81 89 40 91 92 93 94 to6 107 1oE

L. OXIDANTS t 34. N.
1 LL L L L LLL L LL LLH LLL I.L L L L L L L R L L +A
5 LL L L LML L L LL LMH LLL LLLLL L L L R L L L L L
0 LLL LLLL L L L L LH H LL R RMLLL L L L R L L L L R
11 L LL L LMLL L L L LMH L LL LLLLL L L L R L L L L L
16 L R R LLRRL RRR LMH RRR RRLLL L L L R R L L L R

20 L L L LLH LL L LL LMH LLL LLLLL L L L R L L L L M

22 LL L LLHLL L L L LMH LLL LLLLL L L L R L L L L M
24 LL L L LLLL L LL HH H LLM RLLLL L L L R L L L L H
26 LL L L L LHM L L L MHH LL L LLLLL L L L R R E L L M
28 L L L L L Ii L L c L L BHH LLL LLLLL L L L R L L L L B

30 LLL LLML L L L L LMH LL L LLLLL L L L R L L L L M

31 LL L LLMLL L L L LMH L LL LLLLL L L L R L L L L M
35 L L L LLML L L L L LLM L LL LLLLL L L L R L L L L H
37 L RR LLHLL IM RR LMH R RR RHLLL L L L R L L L L R
38 LRR LLMRL 1M RR LM R RRR RBLLL L L L R L L L L R

39 LRR LLMML 1I4 RR LM R RRR RHLLL L L L R L L L L R

44 LL L LL L L L L L L LLH LL R LHLLL L L R R L R L L M
45 LL L L L L L L L LL LMH LL L LLLLL L L R R L R L L L
67 LLR L L L L L 1H RM LLM RRR RRLLL L L L R L L L L L
68 L L L L L L L L 1L L L L L M L LL LLLLL L L L R L L L L M

53 LL L LLL RL IL LL LLM L L L RLLLL L L L R L L L L M

55 L L L LL LML IL L L LLM M M M RLLLL L L L R L L L L M
58 LL L LL L RL IL L L L LM L LL RLLLL L L L R L L L L L
65 LL R LLL RL 1M RM LLM M M M HLLLL L L R R L L L L H
66 LLL LLLLL IL L L LLM LLL LLLLL L L L R L L L L n

67 LLL LLLLL IL L L L LM LL L LLLLL L L L R L L L L B

71 LL L LLL L L IL L L LLM L LH LRLLL L L R R L R L L L
72 LL R LRLLL LML LL H LLL RLLLL L L L R L L L L L
75 RR R LRMLL 1HRH LMH RRR RLRLLM L R R R R L L n
, -
740 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

Reactivity Chart 9. Protection for the Amino Group:

Amides
1. N-Formyl
2. N-Acetyl
3. N-Chloroacetyl
5. N-Trichloroacetyl
6. N-Trifluoroacetyl
7. N-o-Nitrophenylacetyl
8. N-o-Nitrophenoxyacetyl
9. N-Acetoacetyl
12. N-3-Phenylpropionyl
13. N-3-( p-Hydroxyphenyl)propionyl
15. N-2-Methyl-2-(o-nitrophenoxy)propionyl
16. N-2-Methyl-2-(o-phenylazophenoxy)propionyl
17. N-4-Chlorobutyryl
19. N-o-Nitrocinnamoyl
20. N-Picolinoyl
2 1. N-(N’-Acetylmethionyl)
23. N-Benzoyl
29. N-Phthaloyl
3 1. N-Dithiasuccinoyl

(See chart, pp. 741-743.)

Reactivity Chart 9. Protection for the Amino Group: Amides

a
X
PC
.
t! 2;. ‘ri
B X i!
PG i2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 2‘7 28 29 30 31 32 33 34 35 36 37 38
A. AQUEOUS B. BASIC C. NUCLEOPHILIC D.ORGA-. E. CAT. REDN. F.
1 HHHLLLLMHH HLRLLLLL LLHLLML H H L LL L H LL L H LL
2 HMLLLLLLMH LRRRLRLR LLHLLLL HM L LL L L L LL MLL
3 HMLLLLLLHH MRRRLRLR RLHRLRL HMM RL MRRLL H H R
5 HLLLLLMHHH LLRLLRLL RRHMLRL HMM RM RRRLR H H M
6 HLLLLLMHHH LLRLLLLL RRHMLRL HM LMM RRLLL H HM

7 HLLLLLLLMH MRRRLRLR LLHLLLL H H MLL R H RL R H H R

8 HLLLLLLLMH MRRRLLLR MMXMLML H RLLL RRRLR H H R
9 HLLLLLLLHH RRRRRRLR RRHLLLR H RR RR MRLLM L L L
12 HLLLLLLLMH MRRRLRLR LLMLLLL HM L LL L L L L R LL L
13 HLLLLLLLMH RRRRRRLR RLMLLLL H RLLL L LLL R LL L

15 HLLLLLLLMH LLRLLLLL LLMLLLL H RLLL RHRL R H H R

16 HLLLLLLLHH LLRMLHLL LLMLLLL H RRLL RH RRR H H H
17 HLLLLLLLLH MRRRRRLR RLMRLRL HMLRL M RRLL L LL
19 HLLLLLLLMH LLRRLLLL MRMMLML H RRLL R H RLR H H R
20 HLLLLLLLMH LLRLLLLL LLHLLLL HMLL L LL LLR LLL

21 HLLLLLLLMH RRRRRRLR LLHLLLL H RLLL RR RRR LL L

23 HHLLLLLLHH LLRLLLLL LLHLLML HML LL LLL LR LL L
29 HLLLLLLLRH LLRLLLLL LLHLLLL H ML LL LLL L R LL L
31 MLLLLLLMHH LLRRLLLL HHHHLHL HRRMH RRRRR RRR
-l
R Reactivity Chart 9. Protection for the Amino Group: Amides (Continued)

.
FG 39 40 41 42 63 44 45 46 47 48 49 50 51 52 53 54 5556 57 58 59 60 61 62 63 64 65 66 67 68 69 70 31 72 73 74 75 36 77
G. H. HYDRIDE REDN. I. J. K. L. 0x11 &ITS
1 RL LL RLHRLLLHL LLLLLL L LL L LL L LLLLBL HM LL L LL
2 RL L L RLHRLLLHL LLLLLL L LL L LL L LLLLLL LLLLL LL
3 RM LL RMHRLLLHL MMLLLL L H L L LL L LLLLLL LL L LR LL
5 RM L L HMHRHMMHM MMLLLL L H L R RRR LLLLLL LL LL L RL
6 RL L L HMHRHMMHM LLLLLL LML L LL L LLLLRL LL LL L RL

7 R RL L RMHRLLLHL LLLLL L L LL L LM L LLLLLL LL LL L LL

8 RR LL RMHRLLLHL LLLLLL L LL L LL L LLLLLL LLLLL LL
9 R L LL RRHRRRRHR RRMLLL L L L L LL L LHLLML H LLL L RR
12 RL L L RLHRLLLHL LLLLLL L L L L L R L LLLLLL LL LL L LL
13 RL LL RLHRLLLHL LLLLLL L LL R RR R LRLLLM RMML L R H

15 RR LL RMHRLLLHL LLLLLL L LL L L L L LLLLLL LL LL L LL

16 RHRL RLHRRRLHM RLLLLL L RL RRR R LLRMRL RR L RL LL
17 R L L L RMHRLLLHL MMLLLL LHL L LL L LLLLLL L L L L R LL
19 RR L L RMHRLLLHL MMLLLL L LL R RR R RRRLML LRLL L LR
20 RL L L RLHRLLLHL LLLLLL H L H L L R L LLLMRM ML LLL LL

21 RL L L RLHRLLLHL LLLLLL L L L L LL L LRRRRL RLL RL RR

23 RL L L RLHRLLLHL LLLLLL L L L L LL L LLLLLL LL LL L LL
29 R L L L RLHRLLLHL LLLLLL L L H L L L L LLLLLL LL L L L LL
31 RR R L RRHRRLLHR RRLLRL RM L RRR R MRRRRL RRRRR RR
Reactivity Chart 9. Protection for the Amino Group: Amides (Continued)

0”
8
78 79 80 81 82 83 84 85 86 87 88 89 90 91 95 96 97 98 99 100 101-102 103 104 105 LO6 107 108
L. OXIDANTS M. 0. MISCELLANEOUS P.
1 L LM LLLLL LLL L LL LL L LLLLL L L L R R L L H L
2 LL L LLL LL L L L L L L LL L LLLLL L L L R R L L L L
3 LLL L LL L L L LL LLL LLM RLLLL L L L R R L L L L
5 L L L LLLLM LLL L MR L LH RMLLL L L L R IA M L L L
6 LLL LM LLM LLL LM R LLL RLLLL L L L R L L L L L

7 LL L L LLL L L L L L LL LLL LLLLL L L L R R L L L L

8 LL L LLLLL L LL LLL LLL LLLLL L L L R R L L L L
9 LL R LMHML MRM L LM LML RLMLM M L L R R R L M M
12 LLL LLLL L LLL LLL LL L LLLLL L L L R R L L L L
13 M L H MMMM R M RL L LL LLL LLRLR R R L R R R L R L

15 LLL LLLLL LLL L LL L LL LLLLL L L L R L L L L L

16 LL L LLLLR LMR RRR MRR RLLLL L L L R L M L L R
17 LL L LL LL L L LL RRR LL R RLLLL L L L R R L L L L
19 L LM LLLLL L RM L LL RRR LLLLL L L L R L L L L M
20 LLL LL LLL LLL L LL LM M LLLLL L L M R L M L L L

21 L LR L RML L RRL M H H MM L LLLLL L L R R R R L L L

23 LL L L LLL L LL L L L L L L L LLLLL L L L R L L L L L
29 LL L LLLL L LL L L L L LL L LLLLL L L L R L L L L L
31 MM R RMRMR R RL LM H MM H RRLLL L L M R M L L L L
 REACTIVITIES, REAGENTS, AND REACTIVITY CHARTS

Reactivity Chart 10. Protection for the Amino Group:

Special -NH Protective Groups

1. N-Ally1
2. N-Phenacyl
3. N-3-Acetoxypropyl
5. Quaternary Ammonium Salts
6. N-Methoxymethyl
8. N-Benzyloxymethyl
9. N-Pivaloyloxymethyl
12. N-Tetrahydropyranyl
13. N-2,4-Dinitrophenyl
14. N-Benzyl
16. N-o-Nitrobenzyl
17. N-Di( p-methoxyphenyl)methyl
18. N-Triphenylmethyl
19. N-( p-Methoxyphenyl)diphenylmethyl
20. N-Diphenyl-4-pyridylmethyl
2 1. N-2-Picol yl N <Oxide
24. N, N%opropylidene
25. N-Benzylidene
27. N-p-Nitrobenzylidene
28. N-Salicylidene
33. N-(5,5-Dimethyl-3-oxo- 1-cyclohexenyl)
37. N-Nitro
39. N-Oxide
40. N-Diphenylphosphinyl
4 1. N-Dimethylthiophosphinyl
47. N-Benzenesulfenyl
48. N-o-Nitrobenzenesulfenyl
55. N-2,4,6-Trimethylbenzenesulfonyl
56. N-Toluenesulfonyl
57. N-Benzylsulfonyl
59. N-Trifluoromethylsulfonyl
60. N-Phenacylsulfonyl

(See chart, pp. 745-747.)

Reactivity Chart 10. Protection for the Amino Group: Special -NH Protective Groups

0
0 0
m
8 ui
Pi
w 9 ai
2 c( c: 4 A $:
h
& X X X X
a a a a a
Xa
PC; 12 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Dl 32 33 34 35 I6 37 38
A. AQUEOUS B. BASIC C. NUCLEOPHILIC D. 0mNoMET. E. CAT. REDN. P.

i HLLLLLLLLR L R R R L R LLLLLLL L L L L L RR H L R L L L
2 HLLLLLLLLR L R MMMLLRR R RM L R LRRLR H H L
3 HRLLLLMRRR LRRRLRLR RRRLLLL RRL L L L L L L L L L L
5 HLLLLLLLLR LRLMMRLR LLLHLML RRL L R LL L L L H L L
6 HHLLLLLLLL LLLLLLLL LLLLLLL LL L LL LL L L L L L L

HHLLLLLLLL LLLLLLLL LLLLLLL L L L L L H HR L L LLL

HHMLLLMHHH LLRRLLLH HMHLLLL RRL LL L LL L L M LL
HHHHHLLLLL LLLLLLLL LLLLLLL L L L L L L H L L L H H H
HLLLLLLLHH LMRLLLLH MMLHLRL R RMM L RRR L R R RR
HLLLLLLLLL LLLLLLLL LLLLLLL L LL LL H MM LH L L L

16 HLLLLLLLLR LMRLLLLL LLLLLRL H HM M L H H H L R RR R

17 HHHhLLLLLL LLLLLLLL LLLLLLL L L L LL H H H L L H H L
18 HHHHMLLLLL LLLLLLLL LLLLLLL L L L LL H H H LL H H L
19 HHHHMLLLLL LLLLLLLL LLLLLLL LLL LL H H H L L H H L
20 MLLLLLLLLL LLLLLLLL LLLLLLL RRLLL H HH L L H H L

21 HLLLLLLLLR LLRLLHLH LLLLLLL R RL LL RR R R R RR R

24 HHHMLLLLLH LLRLLLLL LLHLLLR RR RM R RR R L R RR R
25 HHHMLLLLMH LLRLLLLL LLHLLLR RR RM R R R?f L R R RR
27 HHHMLLLLLH LMRLLLLL LLHLLRR RR RMM R RR L R RR R
28 HHHMLLLLMH RRRRRRLR RRHLLRR RR R R R R RR L R R RR

33 HHLLLLLLLH LRRRRRLR HRHRLRL RR RMM RR R L R RR R

37 HLLLLLLLLH LLRLLLHH HHRLLLL H H H M L R H H LH H H H
39 HMLLLLLLLH LLRLLMLL LLLLLLL RR L L L H H H H H H H H
40 HHHMLLLLLH LLLLLLLL LLLLLLL L L L L L L M L LL H M L
41 HHHLLLLLLH LLRLLLLL LLLLLLL MMM L L R RR L R H LL

47 HMLLLLLLMH LLRLLLLL LRHHHHH L LL LL RR R L R L L L

48 HHHHLLLLMH LMRLLLLL LRHHHHH RRM ML R RR L R H H R
55 HLLLLLLLLL LLHLLLLL LLLLLLL H H H LL LL LL L H LL
56 HLLLLLLLLL LLHLLLLL LLLLLLL H HH L L L L L LL H L L
57 HMLLLLLLLH RRRRRRLR RRLRLLL H H H LL H HH LL H I4 24

59 HLLLLLLLLH LLHLLLLL LLLLLLL H Ii H H L LLL LL L LM

60 HLLLLLLLRH RRRRRRLR RRRRLRR 11 H H R R H H H L R H n M
Reactivity Chart 10. Protection for the Amino Group: Special -NH Protective Groups
(Continued)

13 44 45 46 47 48 49 50 51 12 53 54 5556 57 58 59 60 il 62 63 64 55 66 67 68 69 70 71 72 73 74 75 76 77
H. HYDRIDE REDN. 1. J. K. L. OXID JTS
1 R L L L LLRRLLLLL L L L LL L R L L RR R R RRRRRR L RR RM MR
2 !? R L R RRRRRRMRR L L L LL L L L L L L L L RRRRRR L RR RM MR
3 R L L L RLLLLLLRM R L L LR L L L L L L L L RRRRRR L RRRM RR
5 L L L L LLLLLLLLL R L L LL L L M L L L L L LLLLLL LLL LH L L
6 L L L L LLLLLLLLL H H H LM L L L L L L L L RRRRRR L RRR&l H R

8 H L L L LLLLLLLLL HH H LML L L R L RRRRRR L R R R M I4 R

9 R L L L RLLLLLLRM H H M LR L L L L L RRRRRR M R R R M RR
12 L L L L LLLLLLLLL H H H LM L L L L L RRRRRR H R R R M
13 R R R L RLLLLLLRM L L L LL L L L L L LMMMHL L L L L L IL"
14 H M L L LLLLLLLLL L L L LL L L L R L RRRRRR L R R R M I4 R

16 H R L L RLLLLLMRM L L L LL L L L R L RRRRRR L R R R M MR
17 H L L L LLLLLLLLL RRLMLL L L R L RRRRRR HRRRM MR
18 H L L L LLLLLLLLL L L L LL L L L L L RRRRRR H RR LM M R
19 H L L L L L L L L L L L L RRLMLL L L L L RRRRRR H RR LM MR
20 H L L L LLLLLLLLL L L L LL L L L L L RRRRRR L RR LM BlR

21 R R R L RMRRMLLMM R L L LL L L L R L L R L RRRRRR L RR RR M R
24 R M L M RLRRLLRRR L L L LM L M M H R R R R RRRRRR HM RL R RR
25 R M L R RLRRMMRRR L L L LM L M M H R R R R RRRRRR HI4 RL R
27 R R L R RLRRMMRRR L L L LM L M M H R R R R RRRRRR HM R L R R"::
28 R M L M RLRRMMRRR R R R LR L M M H R R R R RRRRRR HMRMR RR

33 R L L R RRRRLLMRR LLLLHL L M H R R R R RRRRRL LLRRL L R

37 R R R L RLRRLLRLR LLLLLL L L H R R R R RRRRRR R RR RR RR
39 H H H H HMRRMLMHH R L L LL L L L R L L L L LLLLLL L LL L H LL
40 H L L L MLLLLLLLL L L L LM L L L L L L L L LLLLLL H LL LL
41 H L L L MLLLLLLLL L L L LM L H H H L L L L LLLLLL H LL LL ; L"

47 H H MM HMRRRRMHH H L L LM L H H H L L R L RRRRRR LLLRL R R

H H MH HHRRRRMHH LLL LML H H H L L LL RRRRRR I4 L LN L R R
48
55 H H L L LLLLLLLLL LLLLLL L L L L LRL LLLLLL LLLLL n L
56 HH L L LLLLLLLLL LLLLLL L L L L L R L LLLLLL LLLLL x L
57 ii H L L LLLLLLLLL LLLLLL LLL L Ln L LLLLLL LLLLL n L

n L L L RLLLLLLLL LLLLLL LLL L LLLLLL LLLLL n L

59
H H L L RRRRNHMRR LLLLLL L L L L LLLLLL LLL PL N R
50
Reactivity Chart 10. Protection for the Amino Group: Special -NH Protective Groups
(Continued)

PC 78 79 80 81 82 83 84 85 86 87 68189 b0 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 106
L. OXIDANTS M. N. P.

1 L R R R R R R R RRRLLN R R R LRLLL L L R R L R L L R
2 L M R R R R R R RRRLLH L L L RLRLL L L R R R R L L E
3 L L R R R M L R RRRLLR L L L LLLLL L L R R M R L L E
5 L L L L L L L L LLLRRR L L L LLLLL L L L L L L L R I
6 L L R R R M L R RRRLLM L L L LLLLL L L R R L R L L E

0 L L R R R R M R RRRLLM L L L LLLLL L L R R L R L L E
9 L L R R R M L R RRRLLH L L L LLLLL L L R R L R L L R
12 L L R R R M L R RRRLLH L L L LLLLL L L R R L A L L A
13 L L M L L L L L LLLLMH L L L LLLLL L L M R L H L L R
14 L L R R R R M R RRRLLM L L L LLLLL L L R R L R L L R

16 L L R R R M L R RRRLLR L L L LLLLL L L M R L W L L A
13 L L R R R R M R RRRLLM L L L LLLLL L L R R L R L L A
18 L L R R R H L R RRRLLM L L L LLLLL L L R R L R L L R
19 L L R R R M L R RRRLLM L L L LLLLL L L R R L R L L R
20 L L R R R M L R RRRLLM L L L LMLLR R L R R L R L L R

21 L L R R R R M R RRRRRR L L L klMHH!f H L R R L R L R R
24 R R R R R R R R RRRLMH R R R LLLRR R L M R L M L L R
25 R R R R R R M R RRRLMH R R R RLLLL H L M R t M L L R
27 R R R R R M H R RRRLMH R R R RLLLM R L M R L M L L R
10 R R R R R R M R RRRLMH R R R RLHRR R R M R R R L R R

B3 LRR L R R R M RRRLLM R R R LLLLM H L L R R L L L R

B7 R R R R R R R R RRRLRR R R R RRRLM H L M R R M R R R
B9 L L L L L L L L LLLHRR L L L LLLHH H L L R L L L R R
10 L L L L L M L L LLLLLM L L L LLLLL L L R R L R L L M
11 L L L L R M L L LLLLLH L L L LLLLL L L R R L R L L n

17 R L R R R R L R RRRLMH H L L !fLLtM R L R R R R L L R
18 R L R R R M L M RRRLMR L L L LLLLR R L R R R R L L R
15 L L L L L n L L LLLLMH L L L LLLLL L L L R R R L L M
16 L L L L L n L L LLLLMH L L L LLLLL L L L R R R L L n
I7 LRM L L R M L LLLLMH L L L LLLLL L L L R R M L L M

19 LLLLMR L L L LLLLL L L L R R R L L n
L L L L L L L L
IO L R R L L R R L LLLLNH L L RLRRR R L H R R R L L n
- --L