A new synthetic route to (+/-)-perhydrohistrionicotoxin.
A new synthetic route to (+/-)-perhydrohistrionicotoxin.
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(i-)-全氢组氨酸毒素的新合成路线。
DOI：
10.1002/hlca.19770600720
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发表时间：
1977
影响因子：
1.8
通讯作者：
Y. Ueda
中科院分区：
文献类型：
--
作者：
E. Corey;M. Petrzilka;Y. Ueda
从2-环己烯-1-羧酸乙酯(3)开始，以25%的总收率合成了过氢组氨酸毒素中间体23。这两个关键步骤包括将HOBr加成到肟-烯烃7和溴肟- 17与1-锂-1-丁炔的烷基化反应。后者代表了一种新的方法，立体特异性和位置特异性引入α-位置的亲核丁基等价物到酮羰基。
Starting from ethyl 2-cyclohexen-1-carboxylate (3) the total synthesis of the perhydrohistrionicotoxin intermediate 23 was achieved in 25% overall-yield. The two key steps involve a positionally specific addition of HOBr to the oxime-olefin 7 and the alkylation of bromooxime 17 with 1-lithio-1-butyne. The latter represents a novel method for stereospecific and position-specific introduction of a nucleophilic butyl equivalent in α-position to a ketonic carbonyl group.