Synthetic studies on perophoramidine and the communesins: Construction of the vicinal quaternary stereocenters
Synthetic studies on perophoramidine and the communesins: Construction of the vicinal quaternary stereocenters
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DOI：
10.1021/jo061660a
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发表时间：
2006-11-10
影响因子：
3.6
通讯作者：
Weinreb, Steven M.
中科院分区：
文献类型：
--
作者：
Seo, Jae Hong;Artman, Gerald D., III;Weinreb, Steven M.
报道了一种有效的合成策略，用于安装两个相邻的四元碳中心。关键步骤包括螺旋内酯体系的o -烯丙化/Claisen重排，这是由串联的分子内Heck环化/羰基化形成的。研究了取代基和溶剂对克莱森重排立体化学结果的影响。先前报道的烯丙基螺旋内酯的立体构型为17，现在被修正为31，它在四个碳上具有相同的相对构型。键c -烯丙基旋内酯59承载功能处理所需的communesin核心已构建了9.8:1的非对映体比例。
An efficient synthetic strategy for installation of the two vicinal quaternary carbon centers of the communesins is reported. Key steps include the O-allylation/Claisen rearrangement of spirolactone systems, which are formed by tandem intramolecular Heck cyclization/carbonylation. Substituent and solvent effects on the stereochemical outcome of the Claisen rearrangements have been examined. The stereochemical assignment of the allyl spirolactone previously reported as 17 has now been revised to 31, which has the communesin relative configuration at the quaternary carbons. Key C-allyl spirolactone 59 bearing functional handles required for the communesin core has been constructed with a 9.8:1 diastereomer ratio.