Enantioselective oxidation of di-tert-butyl disulfide with a vanadium catalyst: progress toward mechanism elucidation.
Suzanne A Blum, Robert G Bergman, Jonathan A Ellman
Index: J. Org. Chem. 68(1) , 150-5, (2003)
Full Text: HTML
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.
Related Compounds
Related Articles:
Contact angle goniometry, ellipsometry, XPS, and TOF-SIMS analysis of gold-supported, mixed self-assembled monolayers formed from mixed dialkyl disulfides. Offord DA, et al.
[Langmuir 10(3) , 761-66, (1994)]