The selective conversion of CO_(2)and NH_(3)into valuable nitriles presents significant potential for CO_(2)utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the ...The selective conversion of CO_(2)and NH_(3)into valuable nitriles presents significant potential for CO_(2)utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups,utilizing CO_(2)and NH_(3)as the CN source.Our methodology exhibited exceptional compatibility with diverse functional groups,such as alcohols,ketones,ethers,esters,nitriles,olefins,pyridines,and quinolines,among others,as demonstrated by the successful synthesis of 58 different nitriles.Notably,we achieved high yields in the preparation of bifunctionalized molecules,including intermediates for perampanel,derived from osilylaryl triflates,which are well-known as aryne precursors.Remarkably,no degradation of substrates or formation of aryne intermediates were observed.Mechanistic studies imply that the formation of pentacoordinated silyl isocyanate intermediates is crucial for the key C-C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.展开更多
基金the National Natural Science Foundation of China(Nos.22072167,22202218)the Jiangsu Natural Science Funds for Young Scholar(No.BK20211093)is greatly appreciated.
文摘The selective conversion of CO_(2)and NH_(3)into valuable nitriles presents significant potential for CO_(2)utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups,utilizing CO_(2)and NH_(3)as the CN source.Our methodology exhibited exceptional compatibility with diverse functional groups,such as alcohols,ketones,ethers,esters,nitriles,olefins,pyridines,and quinolines,among others,as demonstrated by the successful synthesis of 58 different nitriles.Notably,we achieved high yields in the preparation of bifunctionalized molecules,including intermediates for perampanel,derived from osilylaryl triflates,which are well-known as aryne precursors.Remarkably,no degradation of substrates or formation of aryne intermediates were observed.Mechanistic studies imply that the formation of pentacoordinated silyl isocyanate intermediates is crucial for the key C-C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
