1,4-Enyne units are ubiquitous skeletons in biologically active molecules and natural products.Especially,they represent versatile building blocks for abundant downstream derivatizations via controllable modifications...1,4-Enyne units are ubiquitous skeletons in biologically active molecules and natural products.Especially,they represent versatile building blocks for abundant downstream derivatizations via controllable modifications of both alkene and alkyne units independently.Recently,great efforts have been made to establish efficient protocols to achieve optically active 1,4-enynes.Considering the enormous application potential of enantioenriched 1,4-enyne units but no related review on this topic has been described,here we aim to provide a comprehensive summary on the catalytic methods established for enantioselective constructions of these intriguing skeletons.According to the reaction types,this review is divided into five parts,including asymmetric allylic substitution,asymmetric propargylic substitution,asymmetric alkynylallylic substitution,asymmetric hydroalkynylation and asymmetric 1,2-addition of alkynes to conjugated imines or ketones.展开更多
基金We are grateful for the financial support from the National Natural Science Foundation of China(NSFC,No.22071262)the Science and Technology Commission of Shanghai Municipality(No.22ZR1475200)Shanghai Rising-Star program(No.20QA1411300).
文摘1,4-Enyne units are ubiquitous skeletons in biologically active molecules and natural products.Especially,they represent versatile building blocks for abundant downstream derivatizations via controllable modifications of both alkene and alkyne units independently.Recently,great efforts have been made to establish efficient protocols to achieve optically active 1,4-enynes.Considering the enormous application potential of enantioenriched 1,4-enyne units but no related review on this topic has been described,here we aim to provide a comprehensive summary on the catalytic methods established for enantioselective constructions of these intriguing skeletons.According to the reaction types,this review is divided into five parts,including asymmetric allylic substitution,asymmetric propargylic substitution,asymmetric alkynylallylic substitution,asymmetric hydroalkynylation and asymmetric 1,2-addition of alkynes to conjugated imines or ketones.