TRIMETHYLSILYL CYANIDE - A REAGENT FOR UMPOLUNG .22. NUCLEOPHILIC ACYLATION OF ALPHA,BETA-UNSATURATED ALDEHYDES BY UMPOLUNG OF ALPHA,BETA-UNSATURATED ALDEHYDES

被引：9
作者：
HUNIG, S
SCHAFER, M
SCHWEEBERG, W
机构：
来源：
CHEMISCHE BERICHTE-RECUEIL | 1993年 / 126卷 / 01期
关键词：
UMPOLUNG; NUCLEOPHILIC ACYLATION; REGIOSELECTIVITY;
D O I：
10.1002/cber.19931260128
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Ambident anions 1a(A) --> 1d(A), obtained from 1a - d by LDA, are treated with alpha,beta-unsaturated aldehydes 2a - c. In all cases the kinetically controlled 1,2/alpha adducts 3 are formed which in contrast to 1,2/alpha adducts with alpha,beta-unsaturated ketones do not rearrange to the thermodynamically stable 1,4/alpha- or 1,4/gamma products 4a and 6. Adducts 4 are smoothly formed if imines of 2 are applied. A thermal oxy-Cope rearrangement transforms adducts 3 into 6. Substantial proportions of 1,2/gamma adducts 5 are produced from 1A and 2 in the presence of magnesium bromide.
引用
收藏
页码：205 / 210
页数：6
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