STEREOCHEMICAL DEPENDENCE OF BASE-CATALYZED CLEAVAGE OF CYCLIC PEROXY KETALS

被引：12

作者：

SNIDER, BB

SHI, ZP

ONEIL, SV

KREUTTER, KD

ARAKAKI, TL

机构：

[1] Department of Chemistry, Brandeis University, Waltham, Massachusetts 02254

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1994年 / 59卷 / 07期

关键词：

D O I：

10.1021/jo00086a022

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Base-catalyzed decomposition of cyclic peroxy ketals 1c, 2c, 14, and 16 shows a strong stereochemical dependence. Isomers 2c and 16 with a pseudoequatorial hydrogen undergo a fast antiperiplanar E2 elimination to afford ene diones 4 and 17 that react further. Ester 1c, with a pseudoaxial hydrogen and a pseudoequatorial acetate side chain, reacts slowly to form the enolate, which undergoes an S(N)2 reaction to give epoxide 3. Peroxy ketals 14 and 15 are stable in base. Peroxy acetals 19 and 20 undergo a faster E2 elimination with loss of the pseudoequatorial acetal proton to provide alkoxide ester 21 that reacts further.

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页码：1726 / 1729

页数：4

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