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A Combined Theoretical and Experimental Investigation on the Enantioselective Oxidation of Aryl Benzyl Sulfides in the Presence of a Chiral Titanium Catalyst
Author(s) -
Naso Francesco,
Capozzi Maria Annunziata M.,
Bottoni Andrea,
Calvaresi Matteo,
Bertolasi Valerio,
Capitelli Francesco,
Cardellicchio Cosimo
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902110
Subject(s) - enantioselective synthesis , catalysis , aryl , chemistry , titanium , computational chemistry , hydrogen bond , density functional theory , reaction mechanism , combinatorial chemistry , organic chemistry , molecule , alkyl
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 hydrogen‐bonding and π 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 π interactions that drive the reaction along the observed stereochemical path is given.