Benzylic C-H activation and C-O bond formation via aryl to benzylic 1,4-palladium migrations

被引：47

作者：

Kesharwani, Tanay ^{[1
]}

Larock, Richard C. ^{[1
]}

机构：

[1] Iowa State Univ, Dept Chem, Ames, IA 50011 USA

来源：

TETRAHEDRON | 2008年 / 64卷 / 26期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1016/j.tet.2008.01.144

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A procedure for benzylic C-H activation has been developed using a palladium 1,4-aryl to benzylic migration as a key step. Carboxylates and phenoxides readily trap the resulting benzylic palladium intermediates obtained from palladium 'through space' migration. Aryl bromides and iodides have been successfully employed in this reaction, furnishing moderate to good yields. The mechanism of this reaction has been studied by deuterium-labeling experiments, which suggest that the migration of palladium from an aryl to a benzylic position occurs reversibly. The reaction conditions developed for the migration process also oxidize the neighboring benzylic alcohols to the corresponding aldehydes and ketones. (C) 2008 Elsevier Ltd. All rights reserved.

引用

页码：6090 / 6102

页数：13

共 67 条

[1]

BACKVALL JE, 2002, HDB ORGANOPALLADIUM, V2, P2853

[2]

BACKVALL JE, 2002, HDB ORGANOPALLADIUM, V2, P1669

[3] CHEMISTRY OF 8-SUBSTITUTED 1-NAPHTHYLMETHYLENES AND 2-SUBSTITUTED BENZYLIDENES - A SIMPLE ENTRY TO 1H-CYCLOBUTA[DE]NAPHTHALENES [J].