Specific cross-dimerization of terminal alkynes via Pd/TMEDA catalysis  

作　　者：Lixin Liu Jianyu Dong Zuqi Fu Lebin Su Shaofeng Wu Qian Shang Shuang-Feng Yin Yongbo Zhou 

机构地区：[1]Advanced Catalytic Engineering Research Center of the Ministry of Education,College of Chemistry and Chemical Engineering,Hunan University,Changsha,410082,China [2]School of Physics and Chemistry,Hunan First Normal University,Changsha,410205,China [3]School of Chemistry and Materials Engineering,Huizhou University,Huizhou,516001,China

出　　处：《Science China Chemistry》2022年第12期2487-2493,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21878072,21706058,22102062,21725602);the Hunan Provincial Natural Science Foundation of China(2020JJ2011);the China Postdoctoral Science Foundation(2019M662774).

摘　　要：The cross-dimerization of terminal alkynes is the most straightforward and attractive approach to differently substituted 1,3-enynes,which are vital structural motifs in natural products,biologically active compounds,and organic functional materials,etc.However,due to the inherent issues of the stereo-,regio-,and chemoselectivity,the strategy is less explored and remains problematic in substrate scope,selectivity,and screening of catalytic system,etc.Herein,a specific cross-dimerization of terminal alkynes is developed under Pd/TMEDA catalysis,which produces a series of gem-1,3-enynes(58 examples)in totally moderate to high yields with outstanding functional group tolerance.A cyclopalladium compound might be the key imtermediate,which performs anti-addition-carbometallation,and leads to the exclusive cross-selectivity.The unprecedented features of the reaction,such as anti-addition-carbometallation,easy control of selectivity,wide range of the donor alkynes,and very simple catalytic conditions,allow it not only a facile and functionally diverse synthesis of 1,3-enynes,but also a substantial progress for the textbook reaction.

关 键 词：cross-dimerization Pd/TMEDA catalysis terminal alkynes gem-1 3-enynes 

分 类 号：O621.251[理学—有机化学]