Ring expansions of 2-alkenylazetidinium salts - a new route to pyrrolidines and azepanes

被引：41

作者：

Couty, Francois ^{[1
]}

Durrat, Francois ^{[1
]}

Evano, Gwilherm ^{[1
]}

Marrot, Jerome ^{[1
]}

机构：

[1] Univ Versailles, UMR 8180, Inst Lavoisier Versailles, F-78035 Versailles, France

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2006年 / 2006卷 / 18期

关键词：

azetidines; azepanes; pyrrolidines; sigmatropic shifts;

D O I：

10.1002/ejoc.200600362

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Series of enantiornerically pure 3-alkenylpyrrolidines, substituted azepanes and stereodefined aminoalkenes were synthesized from 2-alkenylazetidinium trifluoromethanesulfonate salts. The high chemoselectivity of these reactions was found to be strongly dependent both on the nature of the base involved in the process (PhLi or KHMDS) and on the relative cis or trans stereochemistry of the intermediate ammonium ylide. When the yhde and the adjacent alkene are trans, a [1,2] sigmatropic shift occurs exclusively, producing a pyrrolidine with high levels of regioselectivity. On the other hand, clean conversion into 4,5-dehydroazepanes through a 12,3] sigmatropic shift is observed when these two groups are in a cis relationship. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006.

引用

页码：4214 / 4223

页数：10

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