Enantioselective NiH-catalyzed reductive hydrofunctionalization of olefins has attracted much attention in recent years.Using simple chiral ligands,a wide array of functionalized olefins and electrophiles can undergo ...Enantioselective NiH-catalyzed reductive hydrofunctionalization of olefins has attracted much attention in recent years.Using simple chiral ligands,a wide array of functionalized olefins and electrophiles can undergo diverse transformations to afford hydrofunctionalized products,regio-and enantioselectively.These processes avoid the prior preparation of organometallic reagents,and can construct a stereogenic center at a carbon originating either from the olefin or from the electrophile.This review discusses the background,major progress and mechanistic investigations in this reaction.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
Metal-hydride-mediated hydrofunctionalization of alkenes usually features Markovnikov selectivity via the critical step of alkene insertion into the metal-hydride bond.This work demonstrates a relay-hydrogen atom tran...Metal-hydride-mediated hydrofunctionalization of alkenes usually features Markovnikov selectivity via the critical step of alkene insertion into the metal-hydride bond.This work demonstrates a relay-hydrogen atom transfer(relay-HAT)mode rather than an alkene insertion pathway for nickel-catalyzed anti-Markovnikov hydroalkylation of styrenes.This unprecedented mechanistic scenario overrides the conventional Markovnikov selectivity through radical addition to styrene derivatives followed by HAT between the benzyl radical and nickel(II)hydride species.In-depth theoretical studies elucidate the characteristics of this relay-HAT mode from the perspectives of the electronic effect and steric effect.Comparisons of the relay-HAT mode and alkene insertion mode for a series of nickel(II)-hydrideinvolved hydroalkylation reactions of styrene with N-based bidentate or tridentate ligands show the superiority and general applicability of the relay-HAT mode.This will provide practical guidance for ligand selection,as well as reaction design.展开更多
NiH-catalyzed multicomponent reductive hydrofunctionalization of alkenes is an attractive but poorly explored approach to rapidly increasing molecular complexity.In this process,the selective generation of the desired...NiH-catalyzed multicomponent reductive hydrofunctionalization of alkenes is an attractive but poorly explored approach to rapidly increasing molecular complexity.In this process,the selective generation of the desired product can be challenging.Herein,we report that a highly chemo-,regio-and enantioselective reductive hydrocarbonylation of alkenes has been achieved using a chloroformate ester as a source of CO.A wide range of structurally diverseα-hydroxy ketones,privileged structural elements in bioactive molecules and useful building blocks,were obtained from such reactions with high enantiomeric purity.展开更多
Investigation on organocalcium catalysis is just unfolding during the past decade. Beside conventional Ca salts with strong electron-withdrawing counter anions that may serve as Lewis acid catalysts, many Ca complexes...Investigation on organocalcium catalysis is just unfolding during the past decade. Beside conventional Ca salts with strong electron-withdrawing counter anions that may serve as Lewis acid catalysts, many Ca complexes have also been designed recently and found to be good catalysts in activation of element-H （E-H） bonds like transition metal catalysts. These findings are interesting and may attract the interest of the chemists. Due to the great abundance, non-toxicity, and biocompatible features of Ca element, Ca-catalyzed reactions can be of great significance from the viewpoint of industry. This short review summarizes the recent advances on Ca-catalyzed reactions of E-H bonds. We hope that it may provide a useful guide for interested readers from both the academy and industry.展开更多
α-Olefins as aliphatic terminal alkenes could be obtained easily from numerous contemporary synthetic reactions as well as petro-chemical industry,and also found in natural products.Compared to the alkenes attaching ...α-Olefins as aliphatic terminal alkenes could be obtained easily from numerous contemporary synthetic reactions as well as petro-chemical industry,and also found in natural products.Compared to the alkenes attaching the directing groups or activating group,the catalytic asymmetric reaction of unactivated terminal alkenes presents great challenges due to the weak electron effect and small steric hindrance effect.This review mainly summarizes the latest progress of the asymmetric reaction of unactivated terminal olefins since 2016.展开更多
基金Support was provided by NSFC(Nos.21822105,21772087,22001118).
文摘Enantioselective NiH-catalyzed reductive hydrofunctionalization of olefins has attracted much attention in recent years.Using simple chiral ligands,a wide array of functionalized olefins and electrophiles can undergo diverse transformations to afford hydrofunctionalized products,regio-and enantioselectively.These processes avoid the prior preparation of organometallic reagents,and can construct a stereogenic center at a carbon originating either from the olefin or from the electrophile.This review discusses the background,major progress and mechanistic investigations in this reaction.
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supported by the National Natural Science Foundation of China(grants nos.22101265,21903071 and 21822303)China Postdoctoral Science Foundation(grant no.2022M712866)+2 种基金Joint Fund of Key Technologies Research&Development Program of Henan Province(grant no.222301420006)Promotion Projects for Key Research&Development in Henan Province,China(grant no.222102310042)the Ministry of Science and Technology of the People’s Republic of China.
文摘Metal-hydride-mediated hydrofunctionalization of alkenes usually features Markovnikov selectivity via the critical step of alkene insertion into the metal-hydride bond.This work demonstrates a relay-hydrogen atom transfer(relay-HAT)mode rather than an alkene insertion pathway for nickel-catalyzed anti-Markovnikov hydroalkylation of styrenes.This unprecedented mechanistic scenario overrides the conventional Markovnikov selectivity through radical addition to styrene derivatives followed by HAT between the benzyl radical and nickel(II)hydride species.In-depth theoretical studies elucidate the characteristics of this relay-HAT mode from the perspectives of the electronic effect and steric effect.Comparisons of the relay-HAT mode and alkene insertion mode for a series of nickel(II)-hydrideinvolved hydroalkylation reactions of styrene with N-based bidentate or tridentate ligands show the superiority and general applicability of the relay-HAT mode.This will provide practical guidance for ligand selection,as well as reaction design.
基金Support was provided by NSFC (92156004,22271143,22271146)NSF of Jiangsu Province (BK20190281,BK20201245)+1 种基金programs for high-level entrepreneurial and innovative talents introduction of Jiangsu Province (group program),Fundamental Research Funds for the Central Universities (020514380282)Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University.Gao Deng thanks the National College Students'Innovation and Entrepreneurship Training Program (0205145031).
文摘NiH-catalyzed multicomponent reductive hydrofunctionalization of alkenes is an attractive but poorly explored approach to rapidly increasing molecular complexity.In this process,the selective generation of the desired product can be challenging.Herein,we report that a highly chemo-,regio-and enantioselective reductive hydrocarbonylation of alkenes has been achieved using a chloroformate ester as a source of CO.A wide range of structurally diverseα-hydroxy ketones,privileged structural elements in bioactive molecules and useful building blocks,were obtained from such reactions with high enantiomeric purity.
基金supported by the National Natural Science Foundation of China(21202141,21672163)Priority Academic Program Development(PAPD) of Jiangsu Higher Education Institutions+2 种基金Top-notch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP)the Open Project Program of Jiangsu Key Laboratory of Zoonosis(R1509)the Natural Science Foundation of Guangling College(ZKZD17005)
文摘Investigation on organocalcium catalysis is just unfolding during the past decade. Beside conventional Ca salts with strong electron-withdrawing counter anions that may serve as Lewis acid catalysts, many Ca complexes have also been designed recently and found to be good catalysts in activation of element-H （E-H） bonds like transition metal catalysts. These findings are interesting and may attract the interest of the chemists. Due to the great abundance, non-toxicity, and biocompatible features of Ca element, Ca-catalyzed reactions can be of great significance from the viewpoint of industry. This short review summarizes the recent advances on Ca-catalyzed reactions of E-H bonds. We hope that it may provide a useful guide for interested readers from both the academy and industry.
基金supports were provided by National Key R&D Program of China (2021YFA1500200 and 2021YFF0701600)NSFC (22271249)the Fundamental Research Funds for the Central Universities (226-2022-00224 and 226-2023-00115).
文摘α-Olefins as aliphatic terminal alkenes could be obtained easily from numerous contemporary synthetic reactions as well as petro-chemical industry,and also found in natural products.Compared to the alkenes attaching the directing groups or activating group,the catalytic asymmetric reaction of unactivated terminal alkenes presents great challenges due to the weak electron effect and small steric hindrance effect.This review mainly summarizes the latest progress of the asymmetric reaction of unactivated terminal olefins since 2016.
