MICROBIOLOGICAL TRANSFORMATIONS .19. ASYMMETRIC DIHYDROXYLATION OF THE REMOTE DOUBLE-BOND OF GERANIOL - A UNIQUE STEREOCHEMICAL CONTROL ALLOWING EASY ACCESS TO BOTH ENANTIOMERS OF GERANIOL-6,7-DIOL

被引：33

作者：

ZHANG, XM ^{[1
]}

ARCHELAS, A ^{[1
]}

FURSTOSS, R ^{[1
]}

机构：

[1] FAC SCI LUMINY, CHIM ORGAN & BIOORGAN LAB,CNRS,URA 1320, 163 AVE LUMINY,CASE 901, F-13288 MARSEILLE 9, FRANCE

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 12期

关键词：

D O I：

10.1021/jo00012a010

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The microbiological oxygenation of the geraniol N-phenylcarbamate 1 by Aspergillus niger is described, which leads regiospecifically to a formal dihydroxylation of its C(6) = C(7) double bond. By use of different pH values of the incubation medium, it is possible to modulate the stereochemical outcome of this reaction. Thus, 6S diol 3 (ee > 95%) is obtained at pH 2, whereas 6R diol 3 (ee > 95%) is formed at pH 6-7. The mechanism of this reaction has been studied by (O2)-O-18 labeling. It was shown that, in a first step, the 6S epoxide 2 is almost exclusively formed. The second step involves hydrolysis of this key intermediate via a spontaneous acid-catalyzed hydrolysis at pH 2 or an enzymatic hydrolysis at pH 6-7.

引用

页码：3814 / 3817

页数：4

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