DIASTEREOSELECTIVE SYN OR ANTI OPENING OF PROPARGYLIC EPOXIDES - SYNTHESIS OF ALPHA-ALLENIC ALCOHOLS

被引：108

作者：

ALEXAKIS, A

MAREK, I

MANGENEY, P

NORMANT, JF

机构：

[1] Laboratoire de Chimie des Organoéléments, Université P. et M. Curie, CNRS URA 473 Tour 44-45, 75232 Paris Cedex 05

来源：

TETRAHEDRON | 1991年 / 47卷 / 09期

关键词：

D O I：

10.1016/S0040-4020(01)96911-X

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Propargylic epoxides easily react with Grignard reagents and catalytic amounts of copper(I) salt to afford alpha-allenic alcohols. The reaction is highly diastereoselective and its stereochemical outcome (syn or anti isomer) can be fully controlled. The syn diastereomer, probably arising through an addition-elimination mechanism, is better obtained with RMgCl and copper(I) bromide, whereas the anti disastereomer, is better obtained with RMgBr and a complexed copper(I) salt. With RLi and a catalytic amount of copper salt, phenethynyl cyclohexene oxide reacts through reductive lithiation, affording, stereoselectively, an allenyl lithium reagent.

引用

页码：1677 / 1696

页数：20