TANDEM [3,3]-SIGMATROPIC REARRANGEMENTS IN AN ANSAMYCIN - STEREOSPECIFIC CONVERSION OF AN (S)-ALLYLIC ALCOHOL TO AN (S)-ALLYLIC AMINE DERIVATIVE

被引：54

作者：

SCHNUR, RC

CORMAN, ML

机构：

[1] Pfizer Inc., Central Research, Connecticut 06340, Groton

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1994年 / 59卷 / 09期

关键词：

D O I：

10.1021/jo00088a047

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Ansamycin ring modifications in the geldanamycin oncogene inhibitor series were investigated. A carbamate to urea interchange was accomplished with net retention at the 7(S)-center of a geldanamycin analog. This chirally specific transformation was efficiently accomplished by employing tandem [3,3]-sigmatropic rearrangements involving first, the conversion of the allylic 7(S)-alcohol 2b to an allylic 9(S)-thiol, 4b, and then the rearrangement to the allylic 7(S)-isothiocyanate 6, which was carried on to allylic 7(S)-amine derivatives 1a and 1b. This tandem rearrangement strategy may have wide applicability for the preparation of chiral allylic amines from the large array of readily available chiral allylic alcohols.

引用

页码：2581 / 2584

页数：4

共 15 条

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