rdf:type |
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lifeskim:mentions |
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pubmed:issue |
32
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pubmed:dateCreated |
2010-8-11
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pubmed:abstractText |
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)/H(2)O/KOAc or PhI(OAc)(2)/H(2)O/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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pubmed:grant |
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pubmed:commentsCorrections |
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pubmed:language |
eng
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pubmed:journal |
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pubmed:citationSubset |
IM
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pubmed:chemical |
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pubmed:status |
MEDLINE
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pubmed:month |
Aug
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pubmed:issn |
1520-5126
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pubmed:author |
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pubmed:issnType |
Electronic
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pubmed:day |
18
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pubmed:volume |
132
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
11165-70
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pubmed:dateRevised |
2011-9-26
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pubmed:meshHeading |
pubmed-meshheading:20666410-Alcohols,
pubmed-meshheading:20666410-Bromides,
pubmed-meshheading:20666410-Catalysis,
pubmed-meshheading:20666410-Ethylenediamines,
pubmed-meshheading:20666410-Kinetics,
pubmed-meshheading:20666410-Manganese,
pubmed-meshheading:20666410-Models, Molecular,
pubmed-meshheading:20666410-Molecular Conformation,
pubmed-meshheading:20666410-Organometallic Compounds,
pubmed-meshheading:20666410-Oxidation-Reduction,
pubmed-meshheading:20666410-Static Electricity,
pubmed-meshheading:20666410-Stereoisomerism,
pubmed-meshheading:20666410-Substrate Specificity
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pubmed:year |
2010
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pubmed:articleTitle |
Mechanism of the enantioselective oxidation of racemic secondary alcohols catalyzed by chiral Mn(III)-salen complexes.
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pubmed:affiliation |
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
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pubmed:publicationType |
Journal Article,
Research Support, N.I.H., Extramural
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