ASYMMETRIC INDUCTION AND CONFIGURATIONAL CORRELATIONS IN OXIDATIONS AT SULPHUR .V. OXIDATIONS OF OPTICALLY ACTIVE ESTERS OF O-(METHYLTHIO)BENZOIC ACID BY ACHIRAL PEROXY-ACIDS

被引:21
作者
BARBIERI, G
DAVOLI, V
MORETTI, I
MONTANARI, F
TORRE, G
机构
[1] Istituto di Chimica Organica dell'Università
[2] Istituto di Chimica Industriale della Università, Cattedra di Chimica Organica, 20133 Milano
来源
JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC | 1969年 / 05期
关键词
D O I
10.1039/j39690000731
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Oxidation of optically active esters of o-(methylthio)benzoic acid with achiral peroxy-acids (perbenzoic and 2,4,6-trimethylperbenzoic acids) yields mixtures of the corresponding diastereomeric sulphoxides, enriched in one of the components. Hydrolysis affords optically active o-methylsulphinylbenzoic acid. The absolute chirality of the latter depends on the chirality of the inducing alcohol. The optical yields are noticeably higher with the bulkier trimethylperbenzoic acid. The asymmetric induction is interpreted in terms of eclipsing effects of small, medium, and large groups. A correlation model, based on those conformations of the diastereomeric transition states which present the largest difference of steric compression, is suggested.
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页码:731 / +
页数:1
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