Asymmetric synthesis of ABC tricyclic systems in Daphniphyllum alkaloid  

作　　者：Huijing Wang Qiuyan Dong Qinxia Xie Pei Tang 

机构地区：[1]Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry,Sichuan Engineering Laboratory for Plant-Sourced Drug and Sichuan Research Center for Drug Precision Industrial Technology,West China School of Pharmacy,Sichuan University,Chengdu 610041,China [2]Chongqing Key Laboratory of Natural Product Synthesis and Drug Research,School of Pharmaceutical Sciences,Chongqing University,Chongqing 401331,China [3]Skaggs School of Pharmacy and Pharmaceutical Sciences,University of California San Diego,La Jolla 92093-0934,United States

出　　处：《Chinese Chemical Letters》2020年第3期685-688,共4页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(No.21502011);the Fundamental Research Funds for the Central Universities;the Chongqing Science&Technology Commission Project(No.cstc2016jcyjA0168)。

摘　　要：Efficient synthetic routs for the direct and rapid construction of[5-6-6]ABC tricyclic systems of daphmanidin A-type and calyciphylline A-type alkaloids have been successfully developed.For the daphmanidin A-type,the synthesis of[5-6-6]tricyclic framework utilize a HCl-mediated intramolecular Aldol reaction to construct the bicyclo[2.2.2]octane core and a thermal condensation to afford the ABC ring system.In addition,for the calyciphylline A-type,an improved synthesis of ABC[5-6-6]tricyclic system was developed,featuring an introduction of methyl ester group at C2 before the Pd-catalyzed intramolecular oxidative alkylation to construct the desired bowl-shape tricyclic core with stereochemical control.

关 键 词：Daphniphyllum ALKALOID Calyciohylline N 21-Deoxymacropodumine D ABC TRICYCLIC framework INTRAMOLECULAR ALDOL reaction PD-CATALYZED INTRAMOLECULAR oxidative alkylation 

分 类 号：O629.3[理学—有机化学]