An experimental investigation of the enantioselective oxidation of aryl benzyl sulfides by tert-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 hydrogenbonding and p 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 p interactions that drive the reaction along the observed stereochemical path is given

A Combinated Theoretical and Experimental Investigation on the Enantioselective Oxidation of Aryl Benzyl Sulfides in the Presence of a Chiral Titanium Catalyst

CAPOZZI, MARIA ANNUNZIATA MARCELLA;
2009

Abstract

An experimental investigation of the enantioselective oxidation of aryl benzyl sulfides by tert-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 hydrogenbonding and p 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 p interactions that drive the reaction along the observed stereochemical path is given
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11369/8737
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