title: Enantioselective oxidation of di-tert-butyl disulfide with a vanadium catalyst: progress toward mechanism elucidation.
abstract: The mechanism of the oxidation of di-tert-butyl disulfide (1) to the chiral thiosulfinate (2) by H(2)O(2) catalyzed by bis(acetylacetonato)oxovanadium and a chiral Schiff-base ligand (3) has been investigated. Techniques included (51)V NMR spectroscopy, solvent effects on reaction enantioselectivity, and the isolation and full characterization of a 2:1 ligand-to-vanadium catalyst precursor. A model for the dramatic solvent effect on the enantioselectivity of this reaction was developed, based on the identification of a competing nonselective oxidation pathway. From this model, strategies for limiting this competing pathway were developed.
authors.affiliation: Department of Chemistry and Center for New Directions in Organic Synthesis, University of California, Berkeley, California 94720, USA.
authors.forename: Suzanne A
authors.initials: SA
authors.lastname: Blum
authors.forename: Robert G
authors.initials: RG
authors.lastname: Bergman
authors.forename: Jonathan A
authors.initials: JA
authors.lastname: Ellman