对海利波林 C 和 E 的对映选择性全合成。
An enantioselective total synthesis of helioporins C and E.
机构信息
Department of Chemistry, University of Cologne, Greinstrasse 4, 50939 Köln, Germany.
出版信息
Org Lett. 2012 Dec 7;14(23):5996-9. doi: 10.1021/ol302898h. Epub 2012 Nov 13.
A short and enantioselective total synthesis of helioporins C and E, which are bioactive marine diterpenes containing a serrulatane or amphilectane skeleton, was elaborated. The chirogenic step, i.e. a Cu(I)-catalyzed allylic alkylation of a cinnamyl chloride with methylmagnesium bromide, proceeded with virtually complete enantioselectivity (99% ee) in the presence of a chiral phosphine-phosphite ligand. The other stereocenters were diastereoselectively established through Me(2)AlCl-mediated cationic cyclization and Ir-catalyzed hydrogenation.
本文详细描述了海洋二萜类化合物海鞘素 C 和 E 的一种简洁的对映选择性全合成方法，这两种化合物均含有一个蛇菰烷或 Amphilectane 骨架，具有生物活性。在手性配体存在下，通过 Cu(I)催化的肉桂基氯与甲基溴化镁的烯丙基烷基化反应，手性步骤以几乎完全的对映选择性（99%ee）进行。其他立体中心则通过 Me(2)AlCl 介导的阳离子环化和 Ir 催化的氢化反应以非对映选择性方式建立。
Zotero 插件