Nucleohomolytic substitution at boron: A computational approach

被引：19

作者：

Carra, Claudio ^{[1
]}

Scaiano, Juan C. ^{[1
]}

机构：

[1] Univ Ottawa, Dept Chem, Ottawa, ON K1N 6N5, Canada

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2008年 / 2008卷 / 26期

基金：

加拿大自然科学与工程研究理事会;

关键词：

boron; nucleophilic substitution; density functional calculations; radicals;

D O I：

10.1002/ejoc.200800187

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A theoretical investigation is reported on the reaction mechanism for oxygen-centered radical attack on alkyl- and aryl-borane substrates, The model reveals how the mechanism, traditionally considered as a S(H)2 reaction, involves instead nucleophilic attack of the oxygen lone pair on the empty boron p orbital. The single electron on the oxygen is not directly involved in the process, however, as a result of a stereoelectronic effect: the bond aligned with the SOMO orbital is deactivated and the corresponding ligand leaves promptly as a radical species. The overall mechanism can be described as a nucleohomolytic reaction that shares many characteristics with conventional nucleophilic substitution. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008.

引用

页码：4454 / 4459

页数：6