A mechanistic analysis of the Rh-catalyzed intramolecular C-H amination reaction

被引：200

作者：

Fiori, Kristin Williams ^{[1
]}

Espino, Christine G. ^{[1
]}

Brodsky, Benjamin H. ^{[1
]}

Du Bois, J. ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

来源：

TETRAHEDRON | 2009年 / 65卷 / 16期

基金：

美国国家卫生研究院; 美国国家科学基金会;

关键词：

BOND FORMATION REACTIONS; OXIDATIVE CYCLIZATION; HIGHLY EFFICIENT; AMIDATION; INSERTION; AZIRIDINATION; NITRENE; ACTIVATION; RUTHENIUM; DIRHODIUM(II);

D O I：

10.1016/j.tet.2008.11.073

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A detailed mechanistic investigation of the intramolecular dirhodium tetracarboxylate-catalyzed sulfamate ester C-H amination reaction is presented. These studies provide support for the formation of a sulfamate-derived iminoiodinane, which reacts rapidly with the rhodium catalyst to generate a nitrenoid-type oxidant. Reactivity patterns, Hammett analysis, kinetic isotope measurement, and a cyclopropane clock experiment are indicative of a concerted, asynchronous transition structure in the product-determining C-H insertion event. (C) 2008 Published by Elsevier Ltd.

引用

页码：3042 / 3051

页数：10

共 73 条

[71] Enantioselective synthesis of the bromopyrrole alkaloids manzacidin A and C by stereospecific C-H bond oxidation [J].

Wehn, PM ;

Du Bois, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (44) :12950-12951

[72] Mechanism of rhodium-catalyzed carbene formation from diazo compounds [J].

Wong, Freeman M. ;

Wang, Jianbo ;

Hengge, Alvan C. ;

Wu, Weiming .

ORGANIC LETTERS, 2007, 9 (09) :1663-1665

[73] A chiral rhodium carboxamidate catalyst for enantioselective C-H amination [J].

Zalatan, David N. ;

Du Bois, J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (29) :9220-+

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