☆ 4.8 Article

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2010)

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

卷 132, 期 32, 页码 11165-11170

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AMER CHEMICAL SOC

DOI: 10.1021/ja103103d

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Chemistry, Multidisciplinary

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National Institutes of Health

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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.

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