Catalytic Asymmetric Oxidation of tert-Butyl Disulfide. Synthesis of tert-Butanesulfinamides, tert-Butyl Sulfoxides, and tert-Butanesulfinimines
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- 作者：Derek A. Cogan ; Guangcheng Liu ; Kyungjin Kim ; Bradley J. Backes ; and Jonathan A. Ellman
- 刊名：Journal of the American Chemical Society
- 出版年：1998
- 出版时间：August 19, 1998
- 年：1998
- 卷：120
- 期：32
- 页码：8011 - 8019
- 全文大小：258K
- 年卷期：v.120,no.32(August 19, 1998)
- ISSN：1520-5126
文摘
The first example of the catalytic asymmetric oxidation of tert-butyl disulfide (1) is described. Theproduct, tert-butyl tert-butanethiosulfinate (2) is obtained with 91% enantiomeric excess in yields of 
92%on scales as large as 1 mol. The application of H2O2 as stoichiometric oxidant in the presence of 0.25 mol %of VO(acac)2 and 0.26 mol % of a chiral Schiff base ligand, 6a, is both convenient and cost-effective.Thiosulfinate ester 2 is chemically and optically stable and serves as an excellent precursor to chiral tert-butanesulfinyl compounds by the stereospecific nucleophilic displacement of tert-butyl thiolate. Addition ofLiNH2 in liquid ammonia and THF provides tert-butanesulfinamide (3; 91% yield). A single recrystallizationprovides enantiomerically pure 3 in 71-75% overall yield from disulfide 1. Enantiomerically pure thiosulfinateester 2 also reacts readily and stereospecifically with Grignard reagents, organolithiums, lithium amides, andlithium imine salts to provide enantiomerically pure chiral sulfoxides, sulfinamides, and sulfinimines in goodyield.
92%on scales as large as 1 mol. The application of H2O2 as stoichiometric oxidant in the presence of 0.25 mol %of VO(acac)2 and 0.26 mol % of a chiral Schiff base ligand, 6a, is both convenient and cost-effective.Thiosulfinate ester 2 is chemically and optically stable and serves as an excellent precursor to chiral tert-butanesulfinyl compounds by the stereospecific nucleophilic displacement of tert-butyl thiolate. Addition ofLiNH2 in liquid ammonia and THF provides tert-butanesulfinamide (3; 91% yield). A single recrystallizationprovides enantiomerically pure 3 in 71-75% overall yield from disulfide 1. Enantiomerically pure thiosulfinateester 2 also reacts readily and stereospecifically with Grignard reagents, organolithiums, lithium amides, andlithium imine salts to provide enantiomerically pure chiral sulfoxides, sulfinamides, and sulfinimines in goodyield.