USE OF C-13 IN BIOSYNTHETIC-STUDIES - INCORPORATION OF C-13-LABELED ACETATE INTO CHARTREUSIN BY STREPTOMYCES-CHARTREUSIS
USE OF C-13 IN BIOSYNTHETIC-STUDIES - INCORPORATION OF C-13-LABELED ACETATE INTO CHARTREUSIN BY STREPTOMYCES-CHARTREUSIS
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DOI：
10.1139/v77-335
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发表时间：
1977-01-01
影响因子：
1.1
通讯作者：
WRIGHT, JLC
中科院分区：
文献类型：
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作者：
CANHAM, PL;VINING, LC;WRIGHT, JLC
通过补充[1-13C]和[2-13C]乙酸盐的黄曲霉培养物中产生的黄曲霉素的13C NMR光谱检查表明19-C糖苷配基组分完全源自乙酸盐。在从[1,2-13C]乙酸盐富集的黄绿色素的光谱中，由于完整的 13C.sbd.13C 单元的自旋-自旋耦合，16 个碳原子的信号伴随着卫星。耦合对在同核单 13C 频率解耦的帮助下进行匹配。在未偶联的碳原子中，2 个来自乙酸酯的甲基，第 3 个来自乙酸酯的羧基。黄绿色素中配对和不配对的 13C 原子的排列表明糖苷配基源自单个 22-C 聚酮化合物链。环化为类苯并芘中间体，随后环断裂并失去 3 个碳原子，提供了从聚酮化合物到糖苷配基的取代异香豆素结构的合理途径。
Examination by 13C NMR spectroscopy of chartreusin produced in cultures of S. chartreusis supplemented with [1-13C] and [2-13C]acetate showed that the 19-C aglycone component was derived entirely from acetate. In the spectrum of chartreusin enriched from [1,2-13C]acetate the signals for 16 of the carbon atoms were accompanied by satellites due to spin-spin coupling of intact 13C.sbd.13C units. The coupled pairs were matched with the aid of homonuclear single 13C-frequency decoupling. Of the uncoupled C atoms, 2 were derived from methyl groups of acetate and the 3rd came from an acetate carboxyl group. The arrangement of paired and unpaired 13C atoms in chartreusin suggests that the aglycone is derived from a single 22-C polyketide chain. Cyclization to a benzpyrene-like intermediate followed by ring cleavage and loss of 3 C atoms provides a plausible route from the polyketide to the substituted isocoumarin structure of the aglycone.