基于α-溴代酮的催化不对称合成3,3-螺环丙基吲哚酮和乙烯基环丙烷  

Catalytic Enantioselective Syntheses of Functionalized 3,3-Spirocyclopropyl Oxindoles and Vinylcyclopropanes via Ammonium Ylides Generated from α-Bromoketones

作　　者：罗京华 耿玮笙 曹仕轩 贺峥杰[1,2] Luo Jinghua;Geng Weisheng;Cao Shixuan;He Zhengjie(State Key Laboratory of Elemento-organic Chemistry,College of Chemistry,Nankai University,Tianjin 300071;Collaborative Innovation Center of Chemical Science and Engineering(Tianjin),Tianjin 300071)

机构地区：[1]南开大学化学学院,元素有机化学国家重点实验室,天津300071 [2]天津化学化工协同创新中心,天津300071

出　　处：《有机化学》2020年第1期40-52,共13页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21472096,J1103306)资助项目。

摘　　要：在甲基化奎尼丁(20mol%)的催化下,分别实现了α-溴代酮与3-(取代亚甲基)吲哚酮和缺电子1,3-二烯的高度非对映选择性和对映选择性的环丙烷化反应,以46%~99%收率、高达98%ee和20∶1 dr生成相应的3,3-螺环丙基吲哚酮和乙烯基环丙烷.通过催化的氮叶立德策略,成功发展了一种用于上述手性化合物的简便合成方法.Under the catalysis of chiral amine methylated quinidine, highly diastereo-and enantioselective cyclopropanation reactions of α-bromoketones with 3-(substituted methylene) oxindoles and electron-deficient 1,3-dienes have been realized respectively, providing corresponding functionalized 3,3-spirocyclopropyl oxindoles and vinylcyclopropanes in 46%~99% yields with up to 98% ee and up to 20∶1 dr. Thus, a facile and complementary synthetic method for chiral title compounds is successfully develped by the catalytic ammonium ylide strategy.

关 键 词：手性胺 [2+1]环化反应 α-溴代酮 不对称合成 

分 类 号：O621.251[理学—有机化学]