Mechanism of the Enantioselective Oxidation of Racemic Secondary Alcohols Catalyzed by Chiral Mn(III)-Salen Complexes

被引：51

作者：

Brown, M. Kevin ^{[1
]}

Blewett, Megan M. ^{[1
]}

Colombe, James R. ^{[1
]}

Corey, E. J. ^{[1
]}

机构：

[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 32期

基金：

美国国家卫生研究院;

关键词：

HYPERVALENT IODINE(III) REAGENTS; KINETIC RESOLUTION; SALEN COMPLEXES; EPOXIDATION; WATER; HYDROGEN; LIGANDS; ALKENES; FACILE; MODEL;

D O I：

10.1021/ja103103d

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The experiments described here clarify the mechanism and origin of the enantioselectivity of the oxidation of racemic secondary alcohols catalyzed by chiral Mn(III)-salen complexes using HOBr, Br-2/H2O/KOAc or PhI(OAc)(2)/H2O/KBr as a stoichiometric oxidant. Key points of the proposed pathway include (1) the formation of a Mn(V) salen dibromide, (2) its subsequent reaction with the alcohol to give an alkoxy-Mn(V) species, and (3) carbonyl-forming elimination to produce the ketone via a highly organized transition state with intramolecular transfer of hydrogen from carbon to an oxygen of the salen ligand.

引用

页码：11165 / 11170

页数：6

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