Transition-metal-catalyzed cross-electrophile coupling has emerged as a reliable method for constructing carbon–carbon bonds.Herein,we report a general method,cobalt-catalyzed reductive alkynylation,to construct C(sp...Transition-metal-catalyzed cross-electrophile coupling has emerged as a reliable method for constructing carbon–carbon bonds.Herein,we report a general method,cobalt-catalyzed reductive alkynylation,to construct C(sp)-C(sp^(3))and C(sp)-C(sp^(2))bonds.This presented reaction has a broad substrate scope,enabling the efficient cross-electrophile coupling between alkynyl bromides with alkyl halides and aryl or alkenyl(pseudo)halides.This presented reaction is conducted under mild conditions,tolerating many functional groups,thus suitable for the modification and synthesis of biologically active molecules.展开更多
Hydrofunctionalization of alkenes and alkynes is increasingly important in preparing and modifying carbon-centered organic molecules such as pharmaceuticals,agrochemicals,andmaterial precursors.The development of tran...Hydrofunctionalization of alkenes and alkynes is increasingly important in preparing and modifying carbon-centered organic molecules such as pharmaceuticals,agrochemicals,andmaterial precursors.The development of transition-metal-catalysts has revolutionized the hydrofunctionalization of unsaturated hydrocarbons,greatly improving the synthetic efficiency and selectivity of these reactions.In recent years,notable progress has been achieved in low-cost metal-catalyzed alkene and alkyne hydrofunctionalization reactions following the utilization of traditional precious metal catalysts,including palladium,platinum,and rhodium.Earth-abundant cobalt catalysts,which are low in toxicity and exhibit unique reactivity and selectivity,are widely implemented in academic and industrial research.In this review,we highlight recent examples of cobalt-catalyzed hydrofunctionalization of alkenes and alkynes to provide an overview of hydrofunctionalization methods,particularly hydroalkylation reactions.Hydroalkylation reactions greatly expand the scope and utility of cobalt-catalyzed couplings of carbon—carbon bonds.We also highlight the mechanistic considerations and selective determinants involved.We hope our discussion will be informative for future developments in cobalt catalysis and hydrofunctionalization reactions.展开更多
基金the National Natural Science Foundation of China(Nos.22371273,22293011 and T2341001)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2023476)the National Science Foundation of Anhui Province(No.2208085J26)。
文摘Transition-metal-catalyzed cross-electrophile coupling has emerged as a reliable method for constructing carbon–carbon bonds.Herein,we report a general method,cobalt-catalyzed reductive alkynylation,to construct C(sp)-C(sp^(3))and C(sp)-C(sp^(2))bonds.This presented reaction has a broad substrate scope,enabling the efficient cross-electrophile coupling between alkynyl bromides with alkyl halides and aryl or alkenyl(pseudo)halides.This presented reaction is conducted under mild conditions,tolerating many functional groups,thus suitable for the modification and synthesis of biologically active molecules.
基金the National Natural Science Foundation of China(grant nos.22293011 and 22371273)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(grant no.2023476)+2 种基金the National Science Foundation of Anhui Province(grant no.2208085J26)the China Postdoctoral Science Foundation(grant no.BX20230344)the New Cornerstone Science Foundation through the XPLORER PRIZE.
文摘Hydrofunctionalization of alkenes and alkynes is increasingly important in preparing and modifying carbon-centered organic molecules such as pharmaceuticals,agrochemicals,andmaterial precursors.The development of transition-metal-catalysts has revolutionized the hydrofunctionalization of unsaturated hydrocarbons,greatly improving the synthetic efficiency and selectivity of these reactions.In recent years,notable progress has been achieved in low-cost metal-catalyzed alkene and alkyne hydrofunctionalization reactions following the utilization of traditional precious metal catalysts,including palladium,platinum,and rhodium.Earth-abundant cobalt catalysts,which are low in toxicity and exhibit unique reactivity and selectivity,are widely implemented in academic and industrial research.In this review,we highlight recent examples of cobalt-catalyzed hydrofunctionalization of alkenes and alkynes to provide an overview of hydrofunctionalization methods,particularly hydroalkylation reactions.Hydroalkylation reactions greatly expand the scope and utility of cobalt-catalyzed couplings of carbon—carbon bonds.We also highlight the mechanistic considerations and selective determinants involved.We hope our discussion will be informative for future developments in cobalt catalysis and hydrofunctionalization reactions.
基金Project supported by the Sailing Plan of Maoming Green Chemical Industry Research Institute(No.MMGCIRI-2022YFJH-Y-037)the Science and Technology Planning Project of Maoming City(No.2022031)the Special Projects in Key Fields of Ordinary Universities of Guangdong Province(No.2020ZDZX2054)。
