TRICHODIENE BIOSYNTHESIS AND THE STEREOCHEMISTRY OF THE ENZYMATIC CYCLIZATION OF FARNESYL PYROPHOSPHATE
TRICHODIENE BIOSYNTHESIS AND THE STEREOCHEMISTRY OF THE ENZYMATIC CYCLIZATION OF FARNESYL PYROPHOSPHATE
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DOI：
10.1016/0045-2068(85)90027-6
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发表时间：
1985-01-01
影响因子：
5.1
通讯作者：
MURTHY, PPN
中科院分区：
文献类型：
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作者：
CANE, DE;HA, HJ;MURTHY, PPN
反式，反式-[1- 3 H2，12，1 - 3 - 14 C]法呢基焦磷酸（2a）通过从真菌Trichothecium roseum分离的β-二烯合成酶的制备物进行环化，得到β-二烯（5a），化学降解显示其保留了前体的两个C-11氚原子。将1 S-[1- 3 H，12，1 - 3 - 14 C]法呢基焦磷酸（2b）和1 R-[1- 3 H，12，1 - 3 - 14 C]法呢基焦磷酸（2c）与β-二烯合成酶一起孵育，并降解所得标记的β-二烯，5 b和5c，确定了焦磷酸部分从前体的C-1的置换和新的C-1的形成，C键在形成顺丁烯二烯时发生构型的净保留。这些结果是由涉及橙花苷焦磷酸（4）的中间体的异构化-环化机制解释的。
Cyclization of trans,trans-[1-3H2,12,13-14C]farnesyl pyrophosphate (2a) by a preparation of trichodiene synthetase isolated from the fungus, Trichothecium roseum, gave trichodiene (5a), which was shown by chemical degradation to retain both tritium atoms of the precursor at C-11. Incubation of 1S-[1-3H,12,13-14C]farnesyl pyrophosphate (2b) and 1R-[1-3H,12,13-14C]farnesyl pyrophosphate (2c) with trichodiene synthetase and degradation of the resulting labeled trichodienes, 5b and 5c, established that the displacement of the pyrophosphate moiety from C-1 of the precursor and formation of the new C-C bond in the formation of trichodiene takes place with net retention of configuration. These results are accounted for by an isomerization-cyclization mechanism involving the intermediacy of nerolidyl pyrophosphate (4).