STEREOCHEMISTRY IN CARBENOID FORMATION BY BROMINE LITHIUM AND BROMINE ZINC EXCHANGE-REACTIONS OF 1,1-DIBROMOALKENES - HIGHER REACTIVITY OF THE STERICALLY MORE HINDERED BROMINE ATOM

被引：58

作者：

HARADA, T

KATSUHIRA, T

OKU, A

机构：

[1] Department of Chemistry, Kyoto Institute of Technology, Kyoto 606, Matsugasaki, Sakyo-ku

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1992年 / 57卷 / 22期

关键词：

D O I：

10.1021/jo00048a002

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Both lithium and zincate carbenoids (R1-(R2)C=C(Br)M; M = Li and Zn(Bu)2Li) generated by the halogen/metal exchange reaction of 1,1-dibromoalkene 1 with BuLi and (Bu)3ZnLi, respectively, are configurationally stable at low temperatures, but in the presence of excess 1, the lithium carbenoids undergo facile isomerization at the carbenoid carbons. Under kinetically controlled conditions, both the Br/Li and Br/Zn exchange reactions take place preferentially at the sterically more hindered bromine atom of 1.

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页码：5805 / 5807

页数：3

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