ORGANOALUMINUM-CATALYZED REARRANGEMENT OF EPOXIDES - A FACILE ROUTE TO THE SYNTHESIS OF OPTICALLY-ACTIVE BETA-SILOXY ALDEHYDES

被引：104

作者：

MARUOKA, K ^{[1
]}

OOI, T ^{[1
]}

NAGAHARA, S ^{[1
]}

YAMAMOTO, H ^{[1
]}

机构：

[1] NAGOYA UNIV,DEPT APPL CHEM,CHIKUSA,NAGOYA 46401,JAPAN

来源：

TETRAHEDRON | 1991年 / 47卷 / 34期

关键词：

D O I：

10.1016/S0040-4020(01)96153-8

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A new, stereocontrolled rearrangement of epoxy silyl ethers leading to beta-siloxy aldehydes has been effected with stoichiometric use of exceptionally bulky, oxygenophilic methylaluminum bis(4-bromo2,6-di-tert-butylphenoxide) (MABR) under mild conditions. Used in combination with the Sharpless asymmetric epoxidation of allylic alcohols, this rearrangement represents a new approach to the synthesis of various optically active beta-hydroxy aldehydes, useful intermediates in natural product synthesis. The modified organoaluminum reagent, MABR is also applicable to the transformation of a variety of simple epoxides to carbonyl compounds with high efficiency and selectivity. Further, the catalytic version for the rearrangement of epoxy silyl ethers as well as simple epoxides has been newly devised. The scope and limitation of this catalytic method has been clarified with various epoxy substrates.

引用

页码：6983 / 6998

页数：16

共 34 条

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[2]

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