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
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.
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收藏
页码:8705 / 8708
页数:4
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