HIGHLY SELECTIVE ENOLIZATION METHOD FOR HETEROATOM SUBSTITUTED ESTERS - ITS APPLICATION TO THE IRELAND ESTER ENOLATE CLAISEN REARRANGEMENT

被引：33

作者：

HATTORI, K ^{[1
]}

YAMAMOTO, H ^{[1
]}

机构：

[1] NAGOYA UNIV,SCH ENGN,NAGOYA 46401,JAPAN

来源：

TETRAHEDRON | 1994年 / 50卷 / 10期

关键词：

D O I：

10.1016/S0040-4020(01)81109-1

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A method for the stereoselective synthesis of silyl ketene acetals from alpha-siloxy esters, beta-hydroxy esters and alpha-amino esters is described. Internal quench with excess trimethylsilyl chloride of the lithium enolate at -100 degrees C, which is generated using a hindered base, LTMP, leads to the selective formation of E-silyl ketene acetal. In contrast, the deprotonation at -100 degrees C using LHMDS in THF-HMPA (4:1), followed by treatment with tert-butyldimethylsilyl chloride affords the Z-silyl ketene acetal selectively. The method can be applied to the stereoselective reaction of the Ireland ester enolate Claisen rearrangement.

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页码：3099 / 3112

页数：14

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