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

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.