A Diruthenium Catalyst for Selective, Intramolecular Allylic C-H Amination: Reaction Development and Mechanistic Insight Gained through Experiment and Theory

被引：262

作者：

Harvey, Mark Edwin ^{[2
]}

Musaev, Djamaladdin G. ^{[1
]}

Du Bois, J. ^{[2
]}

机构：

[1] Emory Univ, Emerson Ctr Sci Computat, Atlanta, GA 30322 USA

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

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 43期

基金：

美国国家科学基金会;

关键词：

EFFECTIVE CORE POTENTIALS; NITROGEN-ATOM-TRANSFER; MOLECULAR CALCULATIONS; MANGANESE PORPHYRINS; INTERMOLECULAR AMINATION; ALKENE AZIRIDINATION; TERMINAL ALKENES; BOND AMINATION; CHLORAMINE-T; AMIDATION;

D O I：

10.1021/ja203576p

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mixed-valent paddlewheel complex tetrakis-(2-oxypyridinato)diruthenium(II,III) chloride, [Ru-2(hp)(4)Cl], catalyzes intramolecular allylic C-H amination with bis-(homoallylic) sulfamate esters. These results stand in marked contrast to reactions performed with dirhodium catalysts, which favor aziridine products. The following discussion constitutes the first report of C-H amination using complexes such as [Ru-2(hp)(4)Cl] and related diruthenium adducts. Computational and experimental studies implicate a mechanism for [Ru-2(hp)(4)Cl]-promoted C-H amination involving hydrogen-atom abstraction/radical recombination and the intermediacy of a discrete, albeit short-lived, diradical species. The collective data offer a coherent model for understanding the preference of this catalyst to oxidize allylic (and benzylic) C-H bonds.

引用

页码：17207 / 17216

页数：10

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