Studies on the mechanism of action of prekinamycin, a member of the diazoparaquinone family of natural products:: Evidence for both sp2 radical and orthoquinonemethide intermediates
Studies on the mechanism of action of prekinamycin, a member of the diazoparaquinone family of natural products:: Evidence for both sp2 radical and orthoquinonemethide intermediates
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DOI：
10.1021/ja0642616
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发表时间：
2006-09-27
影响因子：
15
通讯作者：
Eastman, Kyle J.
中科院分区：
文献类型：
--
作者：
Feldman, Ken S.;Eastman, Kyle J.
重氮对醌抗生素的假定还原活化化学是用 Bu3Sn-H 和前激霉素二甲醚以及前激霉素本身进行建模的。在芳香族溶剂的各种组合中，无论是否存在亲核体苯甲基硫醇，都可以进行反应，从而分离出自由基捕获芳烃加合物和亲核捕获苯甲基硫醚产物。在这些产物分布研究的基础上，假设首先是环戊烯基自由基，其次是邻醌甲基化物亲电子试剂。
The putative reductive activation chemistry of the diazoparaquinone antibiotics was modeled with Bu3Sn-H and prekinamycin dimethyl ether along with prekinamycin itself. Reaction in various combinations of aromatic solvents, with and without the nucleophile benzylmercaptan present, led to isolation of both radical-trapping arene adducts and nucleophilic capture benzyl thioether products. On the basis of these product distribution studies, the intermediacies of, first, a cyclopentenyl radical and, next, an orthoquinonemethide electrophile are postulated.