Page 215 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 2.24. Conjugate Addition under Aprotic Conditions 187

–
O Li + O O Ph O SECTION 2.6
1 a THF Conjugate Addition by
(CH 3 ) 3 CC CH 2 + PhCH CHCPh (CH 3 ) 3 CCCH 2 CHCH 2 CPh
20 h 90% Carbon Nucleophiles
–
O Li + O O CH 3 O
2 b
(CH 3 ) 2 CHC CHCH 3 + CH 3 CH CHCCH 3 (CH 3 ) 2 CHCCHCHCH 2 CCH 3
88%
CH 3
–
O Li + O O
3 c THF
(CH 3 ) 2 C COCH 3 + 25°C
(CH 3 ) 2 C
83%
CO 2 CH 3
–
4 d O Li + O O CH 2 CH 3
H O
H + H CC(CH 3 ) 3 THF (CH 3 ) 3 COC
OC(CH 3 ) 3
C C CH 2 CC(CH 3 ) 3
–78°C
CH 3 H H
CH 3 CH 2 CH 3 86%
5 e O Li + CH 3
–
CH 3 H H
+ C C
CH 3 THF–HMPA CH 2 CO 2 C 2 H 5
OC 2 H 5 H 5 C 2 O 2 C
–78°C
H H CO 2 C 2 H 5 H 82%
CH 3
O
+
–
6 f H C O Li O H 3 C O
3
CH 2 CHCCH 3
+ CH 2 CCCH 3
SPh
SPh 71%
CH 3 CH 3 CH 3 CH 3
O
–
7 g O Li + CO 2 CH 3 O
SCH 3
CH 3 CH 2 CH COCH 3 + CH 2 C CH 3 CH 2 CHCH 2 CHSCH 3
95%
SCH 3
SCH 3
CN
–
8 h O Li +
CO 2 C 2 H 5 CHCO 2 C 2 H 5
(CH 3 ) 2 CHC C(CH 3 ) 2 + C O
CN C C
CH 3 CH(CH 3 ) 2
CH 3
95%
9 i
O O O CH 3 O
1) LDA, –78°C
(CH 3 ) 2 NCCH(CH 3 ) 2 + CH 3 CH CHCCH 2 CH(CH 3 ) 2 (CH 3 ) 2 NCC(CH 3 ) 2 CHCH 2 CCH 2 CH(CH 3 ) 2
2) NH 4 Cl, H 2 O
78%
10 j Ph Ph
S O N O LDA,THF O N O
CO 2 C 2 H 5 +
S HMPA
S CO 2 C 2 H 5
S
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(1973).
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