Chiral Br?nsted acid-catalyzed asymmetric intermolecular[4+2]annulation of ynamides with para-quinone methides  

作　　者：Hang-Hao Li Ya-Nan Meng Can-Ming Chen Yu-Qi Wang Zhi-Xin Zhang Zhou Xu Bo Zhou Long-Wu Ye 

机构地区：[1]Key Laboratory for Chemical Biology of Fujian Province and State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China [2]Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy,School of Pharmacy,Xuzhou Medical University,Xuzhou 221004,China [3]State Key Laboratory of Elemento-Organic Chemistry,Nankai University,Tianjin 300071,China [4]State Key Laboratory of Organometallic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China

出　　处：《Science China Chemistry》2023年第5期1467-1473,共7页中国科学（化学英文版）

基　　金：supported by the Ministry of Science and Technology(MOST)(2021YFC2100100);the National Natural Science Foundation of China(22125108,22121001,92056104);the President Research Funds from Xiamen University(20720210002);the Natural Science Foundation of Jiangsu Province(BK20211059);the Project of Science and Technology of Xuzhou Government(KC22080);the National Fund for Fostering Talents of Basic Science(NFFTBS)(J1310024)。

摘　　要：Catalytic asymmetric transformations of ynamides have attracted considerable attention in recent years.However,most of them were limited to intramolecular reactions or required metal catalysts.Herein,a chiral Br?nsted acid-catalyzed asymmetric intermolecular[4+2]annulation of ynamides with para-quinone methides(p-QMs)is disclosed,which not only represents the first metal-free protocol for catalytic asymmetric nucleophilic addition of ynamides to electrophiles,but also constitutes the first enantioselective annulation between p-QMs and alkynes.This methodology leads to the practical synthesis of biologically important chiral 4-aryl-3,4-dihydrocoumarins and 4-aryl-coumarins.Preliminary control experiments indicate that the orthohydroxyphenyl substituted p-QMs could isomerize into ortho-quinone methides(o-QMs)in the presence of chiral catalyst,which further react with ynamides via enantioselective[4+2]annulation,to generate the chiral product.

关 键 词：STEREOSELECTIVE metal-free CYCLIZATION YNAMIDES p-QMs 

分 类 号：O621.251[理学—有机化学]