以罕见的7-内型Heck环化反应为关键步骤，对瓜纳卡斯特烯N进行对映选择性全合成。
Enantioselective total synthesis of guanacastepene N using an uncommon 7-endo Heck cyclization as a pivotal step.
作者信息
Iimura Shin, Overman Larry E, Paulini Ralph, Zakarian Armen
机构信息
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, 92697-2025, USA.
出版信息
J Am Chem Soc. 2006 Oct 11;128(40):13095-101. doi: 10.1021/ja0650504.
Abstract
A convergent, enantioselective total synthesis of (+)-guanacastepene N was developed that features a 7-endo Heck cyclization as the key step. In the course of this synthesis, short syntheses of the enantiomerically pure cyclopentenone and cyclohexene building blocks 5 and 6, which constitute A and C ring fragments of guanacastepene N, were developed. These fragments were linked by a challenging conjugate addition reaction that also generated the C11 quaternary carbon stereocenter. Regioselective 7-endo Heck cyclization gave rise to a tricyclic intermediate, which was elaborated to complete the first total synthesis of guanacastepene N and the second enantioselective total synthesis of a guanacastepene natural product.
摘要
开发了一种对映选择性汇聚式全合成（+）-瓜纳卡斯特烯N的方法，其关键步骤为7-内型Heck环化反应。在该合成过程中，开发了对映体纯的环戊烯酮和环己烯结构单元5和6的短合成路线，它们构成了瓜纳卡斯特烯N的A环和C环片段。这些片段通过具有挑战性的共轭加成反应连接，该反应还生成了C11季碳立体中心。区域选择性7-内型Heck环化反应产生了一个三环中间体，经进一步修饰完成了瓜纳卡斯特烯N的首次全合成以及瓜纳卡斯特烯天然产物的第二次对映选择性全合成。
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