Catalytic electronic activation as a tool for the addition of stabilised nucleophiles to allylic alcohols

被引：17

作者：

Black, PJ ^{[1
]}

Edwards, MG ^{[1
]}

Williams, JMJ ^{[1
]}

机构：

[1] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England

来源：

TETRAHEDRON | 2005年 / 61卷 / 05期

关键词：

aluminium; catalytic electronic activation; homogeneous catalysis; hydrogenation; Michael addition;

D O I：

10.1016/j.tet.2004.10.009

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

This paper describes the activation of 2-cyclohexen-1-ol (1) and 2-cyclopenten-1-ol (11) through the use of aluminium-catalysed transfer hydrogenation. The electronically activated substrates are demonstrated to undergo facile conjugate addition and, when the alcohol functional group is subsequently restored in a one-pot procedure, this leads to an indirect addition of nucleophiles to allylic alcohols. This novel methodology has been termed catalytic electronic activation. The aluminium tert-butoxide catalysed conversion of 2-cyclohexen-1-ol (1) into 2-(3-hydroxycyclohexyl)-2-methylmalononitrile (18) and 2-cyclopenten-1-ol (11) into 2-(3-hydroxycyclopentyl)-2-methylmalononitrile (16) in 90 and 60% yield, respectively has been demonstrated through an efficient domino Oppenauer/Michael addition/Meerwein-Ponndorf-Verley process. (C) 2004 Elsevier Ltd. All rights reserved.

引用

页码：1363 / 1374

页数：12

共 43 条

[11] MEERWEIN-PONNDORF-VERLEY REDUCTIONS AND OPPENAUER OXIDATIONS - AN INTEGRATED APPROACH [J].