Page 720 - Advanced Organic Chemistry Part B - Reactions & Synthesis

696 Scheme 8.5. Conjugate Addition and Substitution Reactions of Mixed Organocopper-
Zinc Reagents
CHAPTER 8
Reactions Involving 1 a O O
Transition Metals
(CH ) CCO CH Cu(CN)ZnI +
3 3
2
2
CH 2 O CC(CH )
2
3 3
CH 3
CH 3 97%
2 b Ph
CH CH(CH ) Cu(CN)ZnI TMS Cl CH CH(CH ) CHCH CH O
2 3
2
3
2 3
3
+ PhCH CHCH O
O CC(CH ) O CC(CH ) 92%
2
2
3 3
3 3
3 c O O
1) TMS Cl ) CO CH
CH 2 (CH 2 6 2 3
+ IZn(NC)Cu(CH ) CO CH
3
2
2 5
2) HCl, MeOH
) CH
(CH ) CH 3 (CH 2 4 3
2 4
TBDMSO TBDMSO
OTBDMS OTBDMS 86%
4 d CH 3 CH 3
CH I (CH ) CO CH
CH 3 2 CH 2 3 2 3
Zn, CuI 3
+ CH 2 CHCO CH 3
2
sonification
H H 65%
CF SO 3 CF SO 3
3
3
5 e Cu(CN)ZnBr CO 2 C(CH ) CH CCO C(CH )
2
3 3
2
3 3
C
+ CH 2
CH 2
CH Br 79%
NO 2 2 NO 2
6 a (CH ) CHCHCu(CN)ZnBr CO 2 C(CH 3 ) 3 (CH ) CHCHCH CCO C(CH )
3 2 3 2 2 2 3 3
+ CH 2 C
O CCH 3 CH 2 Br CH CO 2 CH 2 95%
2
3
2
7 f CH 3 CH Ph
3
CH 3 O SCH 3 CH 3
1) ZnCl , LiCl
CO C(CH ) 2
CH 3 CO C(CH )
2 3 3 PhCH MgCl, 4 equiv 2 3 3
2
2) Cu(O SCF ) , 20 mol % NHCO C(CH )
2
3 3
NHCO C(CH ) 3 3 2 96%
2 3 3
8 g O O
CH Li
+ IZn(CH ) Cl 3
2 4
CH 3 SCF CuCN, LiCl CH 3 CH (CH ) Cl
2 4
CH O 3 3 3 88%
3
9 h CH 3 O
1) Zn PhCOCl
CH 3 (CH 2 ) 2 C CPh
3
CH (CH 2 ) 2 C(CH 3 ) 2
2) CuCN, 10 mol %
Br LiBr CH 86%
3
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