Organic Division I, Indian Institute of Chemical Technology, Hyderabad 500 007, India.
J Org Chem. 2010 Feb 5;75(3):748-61. doi: 10.1021/jo9022638.
An efficient, modular, asymmetric synthesis of penaresidin A is disclosed. A beta-protected amino-gamma,delta-unsaturated sulfoxide was prepared by stereoselective addition of the lithio anion of (R)-methyl p-tolyl sulfoxide to an unsaturated sulfinylimine. The pendant sulfoxide group was used as an intramolecular nucleophile to functionalize an alkene regio- and stereoselectively to furnish a bromohydrin, which was employed as the key intermediate in the preparation of the azetidine subunit of penaresidin A. The stereogenic centers of the side chain were introduced by a regioselective opening of an epoxide. Julia-Kocienski olefination was used to couple the azetidine and side chain subunits. The methodology disclosed herein is also useful for the synthesis of ribo- and arabino-phytosphingosines and compounds possessing the amino alcohol moiety.
本文报道了 penaresidin A 的一种高效、模块化、非对映选择性合成方法。通过（R）-甲基对甲苯磺酸酯锂阴离子对不饱和亚磺酰亚胺的立体选择性加成，制备了β-保护的氨基-γ，δ-不饱和亚砜。侧链上的砜基作为亲核试剂，区域和立体选择性地官能化烯烃，生成溴代醇，该溴代醇可作为制备 penaresidin A 的氮杂环丁烷亚基的关键中间体。通过环氧化物的区域选择性开环引入侧链的手性中心。Julia-Kocienski 烯丙基化反应用于连接氮杂环丁烷和侧链亚基。本文所揭示的方法也可用于合成核糖和阿拉伯糖植物鞘氨醇以及具有氨基醇部分的化合物。
