The mechanism of the oxidation of di-tert-butyl disulfide (1) to the chiral thiosulfinate (2) by H2O2 catalyzed by bis(acetylacetonato)oxovanadium and a chiral Schiff-base ligand (3) has been investigated. Techniques included V-51 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.
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Univ Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USAUniv Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USA
Ellman, JA
Owens, TD
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Univ Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USAUniv Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USA
Owens, TD
Tang, TP
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Univ Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USAUniv Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USA
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Univ Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USAUniv Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USA
Ellman, JA
Owens, TD
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Univ Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USAUniv Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USA
Owens, TD
Tang, TP
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Univ Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USAUniv Calif Berkeley, Dept Chem, Ctr New Direct Organ Synth, Berkeley, CA 94720 USA