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

被引：110
|
作者：
Blum, SA
Bergman, RG [1 ]
Ellman, JA
机构：
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Ctr New Direct Organ Synthesis, Berkeley, CA 94720 USA
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 01期
关键词：
D O I：
10.1021/jo0205560
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
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.
引用
收藏
页码：150 / 155
页数：6
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