Probing the electronic demands of transmetalation in the palladium-catalyzed cross-coupling of arylsilanolates

被引：29

作者：

Denmark, Scott E. ^{[1
]}

Smith, Russell C. ^{[1
]}

Chang, Wen-Tau T. ^{[1
]}

机构：

[1] Univ Illinois, Dept Chem, Roger Adams Lab, Urbana, IL 61801 USA

来源：

TETRAHEDRON | 2011年 / 67卷 / 24期

基金：

美国国家卫生研究院;

关键词：

Cross-coupling; Mechanism; Hammett relationship; Transmetalation; Organosilicon; COMPLEXES; STEREOCHEMISTRY; ALKYLBORANES; ELIMINATION; SILANOLATE; MECHANISMS; HALIDES; SULFUR; BORON; ACIDS;

D O I：

10.1016/j.tet.2011.03.066

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The electronic characteristics of coupling partners in the transmetalation step for the cross-coupling reaction of arylsilanolates have been investigated. The ability to interrogate the transmetalation event by in situ preparation of the arylpalladium(II) silanolate intermediate has enabled a Hammett analysis for both the aryl electrophile and arylsilanolate to be conducted. These studies reveal that electron-donating groups on the silicon nucleophile and electron-withdrawing groups on the electrophile accelerate the transmetalation process. (C) 2011 Elsevier Ltd. All rights reserved.

引用

页码：4391 / 4396

页数：6

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