Frankowski Kevin J, Golden Jennifer E, Zeng Yibin, Lei Yao, Aubé Jeffrey
Department of Medicinal Chemistry, University of Kansas, Lawrence, Kansas 66045-7582, USA.
J Am Chem Soc. 2008 May 7;130(18):6018-24. doi: 10.1021/ja800574m. Epub 2008 Apr 9.
A tandem Diels-Alder/azido-Schmidt reaction sequence provides rapid access to the core skeleton shared by several Stemona alkaloids including stenine, neostenine, tuberostemonine, and neotuberostemonine. The discovery and evolution of inter- and intramolecular variations of this process and their applications to total syntheses of (+/-)-stenine and (+/-)-neostenine are described. The stereochemical outcome of the reaction depends on both substrate type and reaction conditions, enabling the preparation of both (+/-)-stenine and (+/-)-neostenine from the same diene/dienophile combination.
串联的狄尔斯-阿尔德反应/叠氮-施密特反应序列能够快速构建几种百部生物碱(包括百部碱、新百部碱、对叶百部碱和新对叶百部碱)所共有的核心骨架。本文描述了该反应分子间和分子内变化的发现、演变及其在(±)-百部碱和(±)-新百部碱全合成中的应用。反应的立体化学结果取决于底物类型和反应条件,使得能够从相同的二烯/亲双烯体组合制备(±)-百部碱和(±)-新百部碱。