BIOSYNTHETIC-STUDIES OF MARINE LIPIDS .24. EXPERIMENTAL DEMONSTRATION OF AN UNPRECEDENTED CYCLOPROPANE-]CYCLOPROPANE REARRANGEMENT IN THE BIOSYNTHESIS OF THE SPONGE STEROL PETROSTEROL

被引：26

作者：

DOSS, GA ^{[1
]}

PROUDFOOT, JR ^{[1
]}

SILVA, CJ ^{[1
]}

DJERASSI, C ^{[1
]}

机构：

[1] STANFORD UNIV,DEPT CHEM,STANFORD,CA 94305

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1990年 / 112卷 / 01期

关键词：

D O I：

10.1021/ja00157a047

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The marine sterol petrosterol (1) is shown to be biosynthesized from 24-methylenecholesterol (4) via an unprecedented cyclopropane → cyclopropane rearrangement presumably involving a protonated species of dihydrocalysterol (3). Such rearrangement was confirmed by feeding [28-14C]-24-methylenecholesterol (4) to the sponge Cribrocalina vasculum and demonstrating that thel4C label, originally at C-28 in 4, has migrated to C-24 in 1. Acid-catalyzed cyclopropane ring opening of 1—a key step in the degradation scheme for locating the label—was studied in detail and shown to be accompanied by an unexpected rearrangement process. © 1990, American Chemical Society. All rights reserved.

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页码：305 / 310

页数：6

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