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.
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收藏
页码：1677 / 1696
页数：20
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