A new mechanistic proposal for the origin of α-homoallylic alcohols in indium-mediated allylation reactions in water

被引：44

作者：

Loh, TP ^{[1
]}

Tan, KT ^{[1
]}

Hu, QY ^{[1
]}

机构：

[1] Natl Univ Singapore, Dept Chem, Singapore 117543, Singapore

来源：

TETRAHEDRON LETTERS | 2001年 / 42卷 / 49期

关键词：

D O I：

10.1016/S0040-4039(01)01884-6

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A new mechanism is proposed for the alpha -regioselective indium-mediated allylation reaction in water. Based on the results and observations obtained from an NMR study, a cross-over experiment and the complete inversion of the stereochemistry of 22 beta gamma -adduct homoallylic sterols to the 22 alpha alpha -adduct homoallylic sterols, it is suggested that the initially formed gamma -adduct undergoes a bond cleavage to generate the parent aldehyde in situ followed by a concerted rearrangement, perhaps a retro-ene reaction followed by a 2-oxonia [3,3]-sigmatropic rearrangement to furnish the alpha -adduct. (C) 2001 Elsevier Science Ltd. All rights reserved.

引用

页码：8705 / 8708

页数：4

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