Chiral rhodium(Ⅱ)-catalyzed asymmetric aldol-type interception of an oxonium ylide to assemble chiral 2,3-dihydropyrans  

作　　者：Aimin Xu Xiaoyu Zhou Rimei Zheng Zhijing Zhang Xinru Yin Kemiao Hong Zhuofeng Ke Yu Qian Wenhao Hu 

机构地区：[1]Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery,School of Pharmaceutical Sciences,Sun Yat-sen University,Guangzhou 510006,China [2]School of Materials Science&Engineering,Sun Yat-sen University,Guangzhou 510006,China

出　　处：《Science China Chemistry》2022年第8期1607-1614,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22001268,21973113,81973176);the Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery(2019B030301005);the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(2016ZT06Y337);the Guangdong Natural Science Fund(2020A1515010614);Key-Area Research and Development Program of Guangdong Province(2022B1111050003)。

摘　　要：A chiral dirhodium complex is an effective and robust catalyst for asymmetric carbene transformations.However,dirhodiumcatalyzed asymmetric ylide interception processes are rare,mainly because of the dissociation of the metal catalyst before the stereo-determining step.Herein,we report a chiral dirhodium(Ⅱ)-catalyzed asymmetric annulation of vinyl diazoesters withα-hydroxyl ketones,which provides an efficient way to form chiral 2,3-dihydropyrans in good yields with excellent diastereoselectivities and enantioselectivities.This article is the first example of the chiral dirhodium complex–controlled asymmetric aldol-type interception of an in situ–formed oxonium ylide.The origin of the high stereoselectivity is well expounded via experimental and computational studies.These generated chiral products exhibit potent antiproliferation activity in three tested cancer cell lines,namely HCT116(colon cancer),A549(lung adenocarcinoma),and SJSA-1(osteosarcoma cancer).

关 键 词：asymmetric aldol-type interception oxonium ylide 2 3-dihydropyrans antiproliferation activity 

分 类 号：O626[理学—有机化学] O643.36[理学—化学]