Page 213 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 2.23. Conjugate Addition by Carbon Nucleophiles 185

1 a O SECTION 2.6
KOC(CH3)3 O
CH 3 10 mol % CH3 Conjugate Addition by
Carbon Nucleophiles
+ H C CHCO CH 3 CH CH CO CH
2
2
t-BuOH 2 2 2 3
53%
CN
3
2 b PhCH CHCN + H C CHCN NH (l) PhCH CCH CH CN
2
2
2
2
2
100%
CONH 2 CONH 2
NaOEt
3 c 12 mol %
CH (CO 2 C 2 H 5 ) 2 + H 2 C CCO 2 C 2 H 5 (C H 5 O 2 C) 2 CHCH 2 CHCO 2 C 2 H 5
2
2
Ph Ph 55 – 60%
CN CN
4 d
KOH
C H + CH CHCN
PhCHCO 2 2 5 2 PhCCH CH CN
2
2
) COH
(CH 3 3 O 69 – 83%
C H
CO 2 2 5
5 e CCH
O 3
R N + – OH
4
+ CH CCH CO C H CHCO C H
2 2 5
2 2 5
3
2
CO CH 3 CO CH 3 86%
2
2
6 f + – CH 3
PhCH N(CH ) OH
2
3 3
(CH ) CHNO + CH 2 CHCO CH 3 O NCCH CH CO CH 3
2
2
2
2
2
2
3 2
CH 3
7 g O NO O
Amberlyst A27 2
(CH ) CHNO + CH 2 CHCCH CH 3 (CH ) CCH CH CCH CH 3
2
2
3 2
3 2
2
2
2
70%
8 h CO CH 3
2
KF CH CH CHCO CH
CH NO + CH 2 C NO 2 2 2 2 3
2
3
O N O
N
O
O
9 i 80%
CH CO C H
2
2 2 5
BrZnCH CO C H + Cl CH CHNO 2 Cl CHCH NO 2
2 2 5
2
2
81%
10 j CH 3 CH 3
O
N 1) dioxane, 16 h O O
+ CH 2 CHCCH 3
2) NaOAc, HOAc, CH CH CCH
H O reflux 2 2 3
2
CH(CH ) CH(CH ) 66%
3 2
3 2
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