期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 15, 期 48, 页码 13417-13426出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200902110
关键词
density functional calculations; enantioselectivity; oxidation; reaction mechanisms; titanium
An experimental investigation of the enantioselective oxidation of aryl benzyl sulfides by tort-butyl hydroperoxide in the presence of a titanium/hydrobenzoin catalyst has shown that these sulfides are ideal substrates for this catalytic system, with negligible interference by the substituents on the aryl groups. A reaction mechanism based on DFT computations has been proposed. The DFT MPWB1K functional was used in the theoretical investigation to account for weak hydrogen-bonding and pi interactions. The computed reaction profile explains the experimentally observed enantioselectivity, which is determined by the thermodynamics of the first phase of the reaction. A detailed discussion of the hydrogen-bonding and pi interactions that drive the reaction along the observed stereochemical path is given.
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