Novel Concise Synthesis of （-）-Clausenamide1  

作　　者：Di Liu Xiaoming Yu Liang Huang 

机构地区：[1]State Key Laboratory of Bioactive Substance and Function of Natural Medicine, Beijing Key Laboratory of ActiveSubstance Discovery and Drugability Evaluation, Institute of Materia Medica, Chinese Academy of Medical Sci-ences & Peking Union Medical College, Beijing 10050, China

出　　处：《Chinese Journal of Chemistry》2013年第3期344-348,共5页中国化学（英文版）

摘　　要：A six-step synthesis of （-）-clausenamide is described. Optically pure （R,E）-1,3-diphenylallylic alcohol was ac-etylated and then subjected to an Ireland-Claisen rearrangement, giving the γ,δ-unsaturated acid, which underwent a substrate-induced stereoselective bromolactonization to afford the expected all-equatorial substituted bromo-δ-lac-one. An unusual chemo-selective aminolysis of the lactone resulted in the formation of a γ,δ-epoxy-amide in stereospecific manner. Base-promoted cyclization of this intermediate and the subsequent Davis oxidation furnished the synthesis, delivering the final product in 〉99% ee and up to 34% overall yield.A six-step synthesis of （-）-clausenamide is described. Optically pure （R,E）-1,3-diphenylallylic alcohol was ac-etylated and then subjected to an Ireland-Claisen rearrangement, giving the γ,δ-unsaturated acid, which underwent a substrate-induced stereoselective bromolactonization to afford the expected all-equatorial substituted bromo-δ-lac-one. An unusual chemo-selective aminolysis of the lactone resulted in the formation of a γ,δ-epoxy-amide in stereospecific manner. Base-promoted cyclization of this intermediate and the subsequent Davis oxidation furnished the synthesis, delivering the final product in 〉99% ee and up to 34% overall yield.

关 键 词：（-）-clausenamide diastereoselective synthesis Ireland-Claisen rearrangement diastereoselectivebromo｜actonization bromo-c^-lactone aminolysis 

分 类 号：TQ623.61[化学工程—精细化工] O621.262[理学—有机化学]