Enantioselective oxidation of di-tert-butyl disulfide with a vanadium catalyst: progress toward mechanism elucidation

Suzanne A Blum; Robert G Bergman; Jonathan A Ellman

doi:10.1021/jo0205560

Enantioselective oxidation of di-tert-butyl disulfide with a vanadium catalyst: progress toward mechanism elucidation

J Org Chem. 2003 Jan 10;68(1):150-5. doi: 10.1021/jo0205560.

Authors

Suzanne A Blum¹, Robert G Bergman, Jonathan A Ellman

Affiliation

¹ Department of Chemistry and Center for New Directions in Organic Synthesis, University of California, Berkeley, California 94720, USA.

PMID: 12515473
DOI: 10.1021/jo0205560

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.