CYCLIZATION OF FARNESYL DIPHOSPHATE TO PENTALENENE - ORTHOGONAL STEREOCHEMISTRY IN AN ENZYME-CATALYZED S-E' REACTION

被引:26
作者
CANE, DE
WEINER, SW
机构
[1] Department of Chemistry, Box H, Brown University, Providence
来源
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE | 1994年 / 72卷 / 01期
关键词
D O I
10.1139/v94-019
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Pentalenene synthase catalyzes the cyclization of farnesyl diphosphate (1) to the sesquiterpene hydrocarbon pentalenene (4). Separate incubations of (4S,8S)-[4,8-H-3(2), 4,8-C-14(2)]farnesyl diphosphate (1a) and (4R,8R)-[4,8-H-3(2), 4,8(14)C(2)]farnesyl diphosphate (1b) with pentalenene synthase isolated from Streptomyces UC5319 and analysis of the derived labeled pentalenenes, 4a and 4b, respectively, by chemical degradation established that H-8si of FPP was lost upon cyclization to pentalenene. Consideration of the plausible conformations of the enzymatic cyclization intermediates indicates that the electrophilic allylic addition-elimination (S-E') reaction in which the C-4,5 bond of pentalenene is formed involves an orthogonal relationship between the C-C bond being formed and the C-H bond that is ultimately broken.
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页码:118 / 127
页数:10
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