The hydrothiolations of alkynes/alkenes with thiols is an atom-economic and thus attractive method for the constructions of C‒S bonds.Here Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposites with varied Ir_(2)S_(3)loadings were o...The hydrothiolations of alkynes/alkenes with thiols is an atom-economic and thus attractive method for the constructions of C‒S bonds.Here Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposites with varied Ir_(2)S_(3)loadings were obtained by one-pot solvothermal method from ZnCl_(2),InCl_(3)and thioacetamide with IrCl_(3).The loading of Ir_(2)S_(3)on the surface of ZnIn_(2)S_(4)promoted the hydrothiolations of alkenes and alkynes,with an optimum performance observed over 0.5 mol%Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposite.Based on the studies on the performance of several other cocatalysts(MoS2,NiS and Pd)loaded ZnIn_(2)S_(4)and the EIS analyses,it was proposed that the superior performance over Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposite can be ascribed to an improved efficiency on the photogeneration of the thiyl radicals by loading Ir_(2)S_(3)as well as its inactivity for photocatalytic hydrogen evolution,a side reaction in the light initiated hydrothiolation reaction over ZnIn_(2)S_(4).This study not only demonstrates an efficient and green strategy to synthesize thiolated products under visible light based on semiconductor photocatalysis,but also provides some guidances for the design and development of photocatalytic systems for light induced organic syntheses.展开更多
The addition reactions of alkenes and alkynes to the H-terminated GaN （0001） surface with a Ga dangling-bond have been studied employing periodic density functional theory （PDFT） calculations. Detailed information...The addition reactions of alkenes and alkynes to the H-terminated GaN （0001） surface with a Ga dangling-bond have been studied employing periodic density functional theory （PDFT） calculations. Detailed information on the reaction pathways of these alkenes and alkynes with H-GaN （0001） surface is provided, which indicates that the reactions contain two steps separated by the metastable intermediates： elementary addition reaction and H-abstraction process. From the energy curves, the reactions are clearly viable in the cases of ethene, styrene and phenylacetylene; while for ethyne, the H-abstraction barrier is higher than the desorption barrier of the intermediate, so the adsorbed C2H2 in intermediate is more likely to be desorbed back into the gas phase than to form a stable adsorbed species. Furthermore, it is obvious that for either alkenes or alkynes, the systems substituted by phenyl have more stable intermediates because π conjugation could improve their stabilities.展开更多
Initiated by CP_2TiCl_2/Fe redox system,2-halotetrafluoroethyl iodides readily reacted with alkynes or alkenes to give 1:1 adducts in good to excellent yields.
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
An efficient, transition-metal free, and practical approach to cis-bis(boryl)alkenes from various alkynes was disclosed in the presence of a catalytic amount of K_2CO_3 under mild conditions. Meanwhile, tetrasubstitut...An efficient, transition-metal free, and practical approach to cis-bis(boryl)alkenes from various alkynes was disclosed in the presence of a catalytic amount of K_2CO_3 under mild conditions. Meanwhile, tetrasubstituted alkenes and phenanthrene derivatives were readily constructed from the target diborylalkenes via Suzuki-Miyaura cross coupling.展开更多
Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which is considered as one of the green and efficient methods and attracts growing research attention. In this review, we summ...Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which is considered as one of the green and efficient methods and attracts growing research attention. In this review, we summarized comprehensively the recent literature reports on the electrochemical oxidative difunctionalization of unsaturated C—C bonds. The reaction types described in this review included electrochemical intermolecular cyclization, electrochemical intramolecular cyclization, and electrochemical difunctionalization of alkenes/alkynes. This review focuses on the discussion of its synthetic generality for the preparation of functionalized compounds and the related electrochemical oxidative reaction mechanism.展开更多
Potassium fluoride on alumina was proved to be an efficient dehydrohalogenating agent for the synthesis of per(poly)fluoroalkyl substituted alkenes and alkynes. The reaction was simple, mild and the yields ranged from...Potassium fluoride on alumina was proved to be an efficient dehydrohalogenating agent for the synthesis of per(poly)fluoroalkyl substituted alkenes and alkynes. The reaction was simple, mild and the yields ranged from good to excellent.展开更多
The dibromination of alkenes and alkynes with bromosuccinimide and sodium bromide catalyzed by FeBr_3 under mild conditions has been developed.The trans-dibromo compounds were exclusively obtained with excellent yields.
New blue-light promoted methods for the addition of iodoacetonitrile(ICH_(2)CN)to alkene/alkynes have been developed.The reaction led to the formation of cyanoalkylated products when conjugated alkene/styrene was used...New blue-light promoted methods for the addition of iodoacetonitrile(ICH_(2)CN)to alkene/alkynes have been developed.The reaction led to the formation of cyanoalkylated products when conjugated alkene/styrene was used.In the case of alkynes and non-conjugated alkenes,iodoalkylation takes place furnishing the corresponding alkenyl iodides and alkyl iodides,respectively.Notably,trans-alkenyl iodides were obtained as the major product.A plausible reaction mechanism is also proposed.展开更多
Hydrogermylation of alkenes and alkynes provides a straightforward synthetic route to organogermanium compounds that have been found applications in organic synthesis,medicinal chemistry,and material science.This pape...Hydrogermylation of alkenes and alkynes provides a straightforward synthetic route to organogermanium compounds that have been found applications in organic synthesis,medicinal chemistry,and material science.This paper reviews the advances in transition-metal-catalyzed hydrogermylation of unsaturated carbon-carbon bonds,including alkenes,alkynes,dienes,and allenes,with the objective of providing readers with the status of the field.Progress,problems,and perspectives in this field are discussed.展开更多
Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoi...Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoichiometric amount of triethylborane (Et3B)/air can efficiently initiate the current free-radical atom transfer reaction.展开更多
The addition and substitution reactions across a variety of alkenes and alkynes have been playing an important role in organic synthesis.In particular,catalyses enabled by homogeneous complexes as well as heterogenous...The addition and substitution reactions across a variety of alkenes and alkynes have been playing an important role in organic synthesis.In particular,catalyses enabled by homogeneous complexes as well as heterogenous nanomaterials have been much received attentions over decades.Along with these blooming progresses in these fields,single-atom site catalysts(SACs)exhibit outstanding performances in terms of reactivity and selectivity,thus providing a new powerful strategy to upgrade these bulk chemicals.Herein,we summarize the reactions of alkenes and alkynes enabled by SACs,in which catalytic hydrogenation,hydrosilylation,hydroboration,hydroformylation,and cross coupling have been included.Moreover,preparations and fine structures of the corresponding SACs have been described,therefore providing a better understanding and overview to address the origin of catalytic activity in the reported examples.展开更多
In the presence of catalytic amount of cesium hydroxide, the hydrothiolation of alkynyl sulfides occurred at room temperature in DMF under nitrogen atmosphere to afford exclusive （Z）-1,2-diorganothio-1-alkene in exc...In the presence of catalytic amount of cesium hydroxide, the hydrothiolation of alkynyl sulfides occurred at room temperature in DMF under nitrogen atmosphere to afford exclusive （Z）-1,2-diorganothio-1-alkene in excellent yields. It could provide a new and expedient way for the preparation of symmetrical and unsymmetrical （Z）-1,2-diorganolthiol-1-alkenes.展开更多
文摘The hydrothiolations of alkynes/alkenes with thiols is an atom-economic and thus attractive method for the constructions of C‒S bonds.Here Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposites with varied Ir_(2)S_(3)loadings were obtained by one-pot solvothermal method from ZnCl_(2),InCl_(3)and thioacetamide with IrCl_(3).The loading of Ir_(2)S_(3)on the surface of ZnIn_(2)S_(4)promoted the hydrothiolations of alkenes and alkynes,with an optimum performance observed over 0.5 mol%Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposite.Based on the studies on the performance of several other cocatalysts(MoS2,NiS and Pd)loaded ZnIn_(2)S_(4)and the EIS analyses,it was proposed that the superior performance over Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposite can be ascribed to an improved efficiency on the photogeneration of the thiyl radicals by loading Ir_(2)S_(3)as well as its inactivity for photocatalytic hydrogen evolution,a side reaction in the light initiated hydrothiolation reaction over ZnIn_(2)S_(4).This study not only demonstrates an efficient and green strategy to synthesize thiolated products under visible light based on semiconductor photocatalysis,but also provides some guidances for the design and development of photocatalytic systems for light induced organic syntheses.
基金Supported by the National Natural Science Foundation of China (No 20673019)
文摘The addition reactions of alkenes and alkynes to the H-terminated GaN （0001） surface with a Ga dangling-bond have been studied employing periodic density functional theory （PDFT） calculations. Detailed information on the reaction pathways of these alkenes and alkynes with H-GaN （0001） surface is provided, which indicates that the reactions contain two steps separated by the metastable intermediates： elementary addition reaction and H-abstraction process. From the energy curves, the reactions are clearly viable in the cases of ethene, styrene and phenylacetylene; while for ethyne, the H-abstraction barrier is higher than the desorption barrier of the intermediate, so the adsorbed C2H2 in intermediate is more likely to be desorbed back into the gas phase than to form a stable adsorbed species. Furthermore, it is obvious that for either alkenes or alkynes, the systems substituted by phenyl have more stable intermediates because π conjugation could improve their stabilities.
文摘Initiated by CP_2TiCl_2/Fe redox system,2-halotetrafluoroethyl iodides readily reacted with alkynes or alkenes to give 1:1 adducts in good to excellent yields.
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(21772046)Program of Innovative Research Team of Huaqiao University(Z14X0047)+2 种基金the Recruitment Program of Global Experts(1000 Talents Plan)the Natural Science Foundation of Fujian Province(2016J01064)Postgraduates’ Innovative Fund in Scientific Research of Huaqiao University for K.Z
文摘An efficient, transition-metal free, and practical approach to cis-bis(boryl)alkenes from various alkynes was disclosed in the presence of a catalytic amount of K_2CO_3 under mild conditions. Meanwhile, tetrasubstituted alkenes and phenanthrene derivatives were readily constructed from the target diborylalkenes via Suzuki-Miyaura cross coupling.
文摘Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which is considered as one of the green and efficient methods and attracts growing research attention. In this review, we summarized comprehensively the recent literature reports on the electrochemical oxidative difunctionalization of unsaturated C—C bonds. The reaction types described in this review included electrochemical intermolecular cyclization, electrochemical intramolecular cyclization, and electrochemical difunctionalization of alkenes/alkynes. This review focuses on the discussion of its synthetic generality for the preparation of functionalized compounds and the related electrochemical oxidative reaction mechanism.
基金Project supported by the National Natural Science Foundation of China.
文摘Potassium fluoride on alumina was proved to be an efficient dehydrohalogenating agent for the synthesis of per(poly)fluoroalkyl substituted alkenes and alkynes. The reaction was simple, mild and the yields ranged from good to excellent.
基金the financial support by Lishui University Opening Foundation for advanced talents
文摘The dibromination of alkenes and alkynes with bromosuccinimide and sodium bromide catalyzed by FeBr_3 under mild conditions has been developed.The trans-dibromo compounds were exclusively obtained with excellent yields.
基金We are grateful to the National Natural Science Foundation of China(Nos.21961045,22061048)the Yunnan Provincial Key Laboratory Construction Plan Funding of Universities and Yunnan Provincial Engineering Research Center Construction Plan Funding of Universities for their financial support.
文摘New blue-light promoted methods for the addition of iodoacetonitrile(ICH_(2)CN)to alkene/alkynes have been developed.The reaction led to the formation of cyanoalkylated products when conjugated alkene/styrene was used.In the case of alkynes and non-conjugated alkenes,iodoalkylation takes place furnishing the corresponding alkenyl iodides and alkyl iodides,respectively.Notably,trans-alkenyl iodides were obtained as the major product.A plausible reaction mechanism is also proposed.
基金supported by the National Key Research and Development Program of the Ministry of Science and Technology of China(2021YFA1500203)Natural Science Foundation of China(22201290,22061160464,and 21821002)Shanghai Sailing Program(22YF1458200).
文摘Hydrogermylation of alkenes and alkynes provides a straightforward synthetic route to organogermanium compounds that have been found applications in organic synthesis,medicinal chemistry,and material science.This paper reviews the advances in transition-metal-catalyzed hydrogermylation of unsaturated carbon-carbon bonds,including alkenes,alkynes,dienes,and allenes,with the objective of providing readers with the status of the field.Progress,problems,and perspectives in this field are discussed.
基金financially supported by the National Natural Science Foundation of China (20825209, 20832008, 20772144)the Chinese Academy of Sciences (Hundreds-Talent Program and Knowledge Innovation Program)
文摘Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoichiometric amount of triethylborane (Et3B)/air can efficiently initiate the current free-radical atom transfer reaction.
基金J.Z.acknowledges Project supported by Shanghai Municipal Science and Technology Major Project(No.2018SHZDZX03)the Program of Introducing Talents of Discipline to Universities(No.B16017).
文摘The addition and substitution reactions across a variety of alkenes and alkynes have been playing an important role in organic synthesis.In particular,catalyses enabled by homogeneous complexes as well as heterogenous nanomaterials have been much received attentions over decades.Along with these blooming progresses in these fields,single-atom site catalysts(SACs)exhibit outstanding performances in terms of reactivity and selectivity,thus providing a new powerful strategy to upgrade these bulk chemicals.Herein,we summarize the reactions of alkenes and alkynes enabled by SACs,in which catalytic hydrogenation,hydrosilylation,hydroboration,hydroformylation,and cross coupling have been included.Moreover,preparations and fine structures of the corresponding SACs have been described,therefore providing a better understanding and overview to address the origin of catalytic activity in the reported examples.
基金Project supported by the National Natural Science Foundation of China （Nos. 21071152, 20372020）.
文摘In the presence of catalytic amount of cesium hydroxide, the hydrothiolation of alkynyl sulfides occurred at room temperature in DMF under nitrogen atmosphere to afford exclusive （Z）-1,2-diorganothio-1-alkene in excellent yields. It could provide a new and expedient way for the preparation of symmetrical and unsymmetrical （Z）-1,2-diorganolthiol-1-alkenes.
