The stereospecific carbocupration of terminal alkynes via higher order cuprates to give 1,1'-disubstituted olefins with 99% configuration purity is described. Its synthetic utility as a general method for the prep...The stereospecific carbocupration of terminal alkynes via higher order cuprates to give 1,1'-disubstituted olefins with 99% configuration purity is described. Its synthetic utility as a general method for the preparation of substituted olefins is further illustrated by the direct synthesis of (±)-ipsenol and (E)-β-farnesene with highly geometric purity of the carbon-carbon double bond.展开更多
The efficient utilization of visible light catalysts for organic reactions necessitates not only the effective separation of photogenerated electrons and holes to participate in the reaction,but also their ability to ...The efficient utilization of visible light catalysts for organic reactions necessitates not only the effective separation of photogenerated electrons and holes to participate in the reaction,but also their ability to form key intermediates with reactant molecules.The present study successfully synthesized a crusiform-like mesoporous structure of nitrogen-doped carbon-coated Cu_(2)O/Cu(Cu_(2)O/Cu/N-C)with a Cu_(2)O/dual electron acceptor interface using etched HKUST-1 as the precursor.A series of theoretical and experimental studies have demonstrated that the Cu_(2)O/Cu/N-C interface in the photocatalytic homo-coupling of terminal alkynes not only effectively enhances the separation of photogenerated electron−hole pairs,but also facilitates the formation of the key intermediate[Cu_(2)O/Cu/N-C]-phenylacetylide and promotes the rearrangement of its internal charges.As a result,the homo-coupling reaction can be effectively facilitated.The primary reason for the functional role of Cu_(2)O/Cu/N-C interface lies in the downward bending of energy band from Cu_(2)O to N-doped C layers,induced by the different work functions of Cu_(2)O,Cu and N-doped C layers.Consequently,Cu_(2)O/Cu/N-C photocatalysts demonstrate exceptional photocatalytic activity in the homo-coupling reaction of terminal alkynes under blue-light irradiation and air atmosphere.The present study presents a novel research methodology for the development of highly efficient visible light catalysts to facilitate organic reactions in future applications.展开更多
The hydroarylation reaction of terminal alkynes with arylboronic acids catalyzed by low(400 ppm) loadings of palladium has been developed. The reaction is broad in scope and high-yielding, even on multigram scale. It ...The hydroarylation reaction of terminal alkynes with arylboronic acids catalyzed by low(400 ppm) loadings of palladium has been developed. The reaction is broad in scope and high-yielding, even on multigram scale. It is suitable for the synthesis of alkenes labeled with deuterium, and for the late-stage modification of bioactive molecules.展开更多
Mercurous chloride catalyzed Mannich condensation of terminal alkynes with secondary amines and aldehydes has been developed. The reaction generated β-aminoalkynes in good yields.
A novel platinum-catalyzed asymmetric ring-opening reaction of oxabenzonorbornadiene with terminal alkynes is described.The reaction affords optically active cis-2-alkynyl-1,2-dihydronaphthalen-1-ols in moderate yield...A novel platinum-catalyzed asymmetric ring-opening reaction of oxabenzonorbornadiene with terminal alkynes is described.The reaction affords optically active cis-2-alkynyl-1,2-dihydronaphthalen-1-ols in moderate yields with good enantioselectivity in the presence of catalytic amounts of Pt(COD)Cl_(2)/(S)-BINAP and an excess of zinc powder.The products were obtained exclusively with the relative cis-configuration of the ring substituents and the prevalent(1R,2S)-configuration of the stereocenters,as determined by single crystal X-ray diffraction analysis.展开更多
The cross-dimerization of terminal alkynes is the most straightforward and attractive approach to differently substituted 1,3-enynes,which are vital structural motifs in natural products,biologically active compounds,...The cross-dimerization of terminal alkynes is the most straightforward and attractive approach to differently substituted 1,3-enynes,which are vital structural motifs in natural products,biologically active compounds,and organic functional materials,etc.However,due to the inherent issues of the stereo-,regio-,and chemoselectivity,the strategy is less explored and remains problematic in substrate scope,selectivity,and screening of catalytic system,etc.Herein,a specific cross-dimerization of terminal alkynes is developed under Pd/TMEDA catalysis,which produces a series of gem-1,3-enynes(58 examples)in totally moderate to high yields with outstanding functional group tolerance.A cyclopalladium compound might be the key imtermediate,which performs anti-addition-carbometallation,and leads to the exclusive cross-selectivity.The unprecedented features of the reaction,such as anti-addition-carbometallation,easy control of selectivity,wide range of the donor alkynes,and very simple catalytic conditions,allow it not only a facile and functionally diverse synthesis of 1,3-enynes,but also a substantial progress for the textbook reaction.展开更多
A microwave enhanced, solventless Mannich condensation of terminal alkynes, primary amines with paraformaldehyde on cuprous iodide doped alumina has been investigated. The structures of products depend on the ratio o...A microwave enhanced, solventless Mannich condensation of terminal alkynes, primary amines with paraformaldehyde on cuprous iodide doped alumina has been investigated. The structures of products depend on the ratio of alkyne to amine and paraformaldehyde.展开更多
FeCl3- and GaCl3-catalyzed dehydrative coupling reactions of chromone-derived Morita-Baylis-Hillman (MBH) alcohols with terminal alkynes were developed. The reactions provided exclusively a-regioselective and acetyl...FeCl3- and GaCl3-catalyzed dehydrative coupling reactions of chromone-derived Morita-Baylis-Hillman (MBH) alcohols with terminal alkynes were developed. The reactions provided exclusively a-regioselective and acetylene-substituted products in good yields.展开更多
Bottom-up approach to constructing low-dimensional nanostructures on surfaces with terminal alkynes has drawn great interest because of its potential applications in fabricating advanced functional nanomaterials. The ...Bottom-up approach to constructing low-dimensional nanostructures on surfaces with terminal alkynes has drawn great interest because of its potential applications in fabricating advanced functional nanomaterials. The diversity of the achieved products manifests rich chemistry of terminal alkynes and hence careful linking strategies and proper controlling methodologies are required for selective preparations of high-quality target nanoarchitectures. This review summarizes various on-surface linking strategies for terminal alkynes, including non-bonding interactions as well as organometallic and covalent bonds, and presents examples to show effective control of surface assemblies and reactions of terminal alkynes by variations of the precursor structures, substrates and activation modes. Systematic studies of the on-surface linkage of terminal alkynes may help efficient and predictable preparations of surface nanomaterials and further understanding of surface chemistry.展开更多
Reaction of perfluoroalkyl iodides with a series of alkynes under sulfinatodehalogenation condition gave a mixture of E/Z adducts very readily in high yield, thus constituted a mild, convenient and effective new metho...Reaction of perfluoroalkyl iodides with a series of alkynes under sulfinatodehalogenation condition gave a mixture of E/Z adducts very readily in high yield, thus constituted a mild, convenient and effective new method for the addition of perfluoroalkyl iodides to alkynes. Under the same con- dition, in the presence of 1-hexyne perfluoroalkyl bromide and 1,1,1-trichlorotrifluoroethane reacted only to give sulfinates as the major products. A radical mechanism was proposed for the addition reaction.展开更多
(E)-α-Iodovinyl sulfides 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol % of Pd(PPh3)4 and 10 mol % of CuI to afford the correspo...(E)-α-Iodovinyl sulfides 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol % of Pd(PPh3)4 and 10 mol % of CuI to afford the corresponding 1, 3-enynylsulfides 3 stereospecifically in high yields.展开更多
(E)-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically af...(E)-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically afford the corresponding (Z)-2-sulfonyl-substituted 1,3-enynes 3 in high yields.展开更多
The mixture of cesium hydroxide and terminal alkynes in dry DMF in the presence of 4 A molecular sieves was stirred for 3.0 h at room temperature under N2, then aryltellurenyl bromide in THF was added, and the reactio...The mixture of cesium hydroxide and terminal alkynes in dry DMF in the presence of 4 A molecular sieves was stirred for 3.0 h at room temperature under N2, then aryltellurenyl bromide in THF was added, and the reaction mixture was stirred for 2.0 h. Alkynyl tellurides were obtained in about 90% yields by flash chromatography.展开更多
The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and...The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and Au)catalysis has emerged as a synthetic strategy for a wide range of organic chemical reactions in past decades.In coinage-metal-catalyzed carboxylation,CO_(2)is adopted as a carboxylation reagent,while coinage-metal salts,complexes,and nanoparticles(NPs)serve as a Lewis acid catalyst to activate unsaturated chemicals,particularly alkynes.This mini-review focuses on the recent advances of coinage-metal-catalyzed carboxylation of terminal alkynes with CO_(2).Other respects,such as the role of bases,the influence of trace water,and solvent effects are also highlighted.展开更多
Although precious transition metals such as palladium,platinum,and iridium are widely used in hydrogenation reactions,the earth-abundant transition metal-catalyzed highly selective semi-hydrogenation of terminal alkyn...Although precious transition metals such as palladium,platinum,and iridium are widely used in hydrogenation reactions,the earth-abundant transition metal-catalyzed highly selective semi-hydrogenation of terminal alkynes to terminal alkenes remains poorly developed and a challenge.Herein we demonstrate the excellent selective,cost-effective semi-hydrogenation of terminal alkynes via a novel graphene encapsulated Ni@N/C catalyst.The graphene layer encapsulated nano-catalyst Ni@N/C could significantly avoid metal leaching and improve the stability of the catalyst.The strong interaction of nitrogen with the Ni nanoparticles regulates the activity of Ni towards selective semi-hydrogenation of terminal alkynes.Substrates having un-functionalized as well as functionalized substituents,and substrates having sensitive functional groups(olefins,ketones)which pose a challenge to hydrogenate,were semi-hydrogenated with excellent conversion(up to 99%)and selectivity(up to 99%)under optimized reaction conditions.展开更多
A facile and direct fluorination process of alkynes and diynes was developed, in the presence of n-butyllithium, the reaction of a series of terminal alkynes and diynes with the electrophilic fluorinating reagent (N...A facile and direct fluorination process of alkynes and diynes was developed, in the presence of n-butyllithium, the reaction of a series of terminal alkynes and diynes with the electrophilic fluorinating reagent (NFSI) proceeded to afford various 1-fluoroalkynes and 1-fluoro-l,3-diynes in moderate to high yields.展开更多
A Sonogashira coupling reaction of aromatic halides with terminal alkynes in the presence of palladium powder, potassium fluoride, cuprous iodide and triphenylphosphine in methanol, giving the corresponding coupling p...A Sonogashira coupling reaction of aromatic halides with terminal alkynes in the presence of palladium powder, potassium fluoride, cuprous iodide and triphenylphosphine in methanol, giving the corresponding coupling products aryl alkynes in good to excellent yields, was investigated.展开更多
基金Supported by the National Natural Science Foundation of China
文摘The stereospecific carbocupration of terminal alkynes via higher order cuprates to give 1,1'-disubstituted olefins with 99% configuration purity is described. Its synthetic utility as a general method for the preparation of substituted olefins is further illustrated by the direct synthesis of (±)-ipsenol and (E)-β-farnesene with highly geometric purity of the carbon-carbon double bond.
基金supported by the Xuzhou Key Research and Development Program(Social Development)(No.KC23298)the National Natural Science Foundation of China(No.22271122)+1 种基金the Natural Science Foundation of Jiangsu Province(No.BK20211549)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX23_2903).
文摘The efficient utilization of visible light catalysts for organic reactions necessitates not only the effective separation of photogenerated electrons and holes to participate in the reaction,but also their ability to form key intermediates with reactant molecules.The present study successfully synthesized a crusiform-like mesoporous structure of nitrogen-doped carbon-coated Cu_(2)O/Cu(Cu_(2)O/Cu/N-C)with a Cu_(2)O/dual electron acceptor interface using etched HKUST-1 as the precursor.A series of theoretical and experimental studies have demonstrated that the Cu_(2)O/Cu/N-C interface in the photocatalytic homo-coupling of terminal alkynes not only effectively enhances the separation of photogenerated electron−hole pairs,but also facilitates the formation of the key intermediate[Cu_(2)O/Cu/N-C]-phenylacetylide and promotes the rearrangement of its internal charges.As a result,the homo-coupling reaction can be effectively facilitated.The primary reason for the functional role of Cu_(2)O/Cu/N-C interface lies in the downward bending of energy band from Cu_(2)O to N-doped C layers,induced by the different work functions of Cu_(2)O,Cu and N-doped C layers.Consequently,Cu_(2)O/Cu/N-C photocatalysts demonstrate exceptional photocatalytic activity in the homo-coupling reaction of terminal alkynes under blue-light irradiation and air atmosphere.The present study presents a novel research methodology for the development of highly efficient visible light catalysts to facilitate organic reactions in future applications.
基金financial support from the National Natural Science Foundation of China (No. 21472033)the National Key R&D Program of China (No. 2018YFB1501604)the Fundamental Research Funds for the Central Universities (No. PA2020GDKC0021)。
文摘The hydroarylation reaction of terminal alkynes with arylboronic acids catalyzed by low(400 ppm) loadings of palladium has been developed. The reaction is broad in scope and high-yielding, even on multigram scale. It is suitable for the synthesis of alkenes labeled with deuterium, and for the late-stage modification of bioactive molecules.
基金Project supported by the National Natural Science Foundation of China (No. 20372024), the Excellent Scientist Foundation of Anhui Province (No.04046080), the Natural Science Foundation of the Education Department of Anhui Province (No. 2002kj254zd), the Scientific Research Foundation for the Returned 0verseas Chinese Scholars, the Ministry of Education of China (No. 2002247), the Excellent Young Teacher Program of the Ministry of Education of China (No. 2024) and the Key Project of Science and Technology of the Ministry of Education of China (No. 0204069).
文摘Mercurous chloride catalyzed Mannich condensation of terminal alkynes with secondary amines and aldehydes has been developed. The reaction generated β-aminoalkynes in good yields.
基金the National Natural Science Foundation of China(No.41376149)the Guangzhou Pearl River New Star Plan of Science and Technology Program(No.2012J2200015).
文摘A novel platinum-catalyzed asymmetric ring-opening reaction of oxabenzonorbornadiene with terminal alkynes is described.The reaction affords optically active cis-2-alkynyl-1,2-dihydronaphthalen-1-ols in moderate yields with good enantioselectivity in the presence of catalytic amounts of Pt(COD)Cl_(2)/(S)-BINAP and an excess of zinc powder.The products were obtained exclusively with the relative cis-configuration of the ring substituents and the prevalent(1R,2S)-configuration of the stereocenters,as determined by single crystal X-ray diffraction analysis.
基金supported by the National Natural Science Foundation of China(21878072,21706058,22102062,21725602)the Hunan Provincial Natural Science Foundation of China(2020JJ2011)the China Postdoctoral Science Foundation(2019M662774).
文摘The cross-dimerization of terminal alkynes is the most straightforward and attractive approach to differently substituted 1,3-enynes,which are vital structural motifs in natural products,biologically active compounds,and organic functional materials,etc.However,due to the inherent issues of the stereo-,regio-,and chemoselectivity,the strategy is less explored and remains problematic in substrate scope,selectivity,and screening of catalytic system,etc.Herein,a specific cross-dimerization of terminal alkynes is developed under Pd/TMEDA catalysis,which produces a series of gem-1,3-enynes(58 examples)in totally moderate to high yields with outstanding functional group tolerance.A cyclopalladium compound might be the key imtermediate,which performs anti-addition-carbometallation,and leads to the exclusive cross-selectivity.The unprecedented features of the reaction,such as anti-addition-carbometallation,easy control of selectivity,wide range of the donor alkynes,and very simple catalytic conditions,allow it not only a facile and functionally diverse synthesis of 1,3-enynes,but also a substantial progress for the textbook reaction.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 0 172 0 18) theExcellentScientistFoundationofAnhuiProvince (No .2 0 0 10 40 ) +1 种基金theNaturalScienceFoundationoftheEducationDepartmentofAnhuiProvince (No .2 0 0 2kj2 5 4ZD) theSci e
文摘A microwave enhanced, solventless Mannich condensation of terminal alkynes, primary amines with paraformaldehyde on cuprous iodide doped alumina has been investigated. The structures of products depend on the ratio of alkyne to amine and paraformaldehyde.
基金Project supported by the National Natural Science Foundation of China, Ministry of Science and Technology (973 Program, No. 2011CB808600) and the Chinese Academy of Sciences.
文摘FeCl3- and GaCl3-catalyzed dehydrative coupling reactions of chromone-derived Morita-Baylis-Hillman (MBH) alcohols with terminal alkynes were developed. The reactions provided exclusively a-regioselective and acetylene-substituted products in good yields.
基金jointly supported by National Natural Science Foundation of China (NSFC) (Nos. 91527303, 21333001)
文摘Bottom-up approach to constructing low-dimensional nanostructures on surfaces with terminal alkynes has drawn great interest because of its potential applications in fabricating advanced functional nanomaterials. The diversity of the achieved products manifests rich chemistry of terminal alkynes and hence careful linking strategies and proper controlling methodologies are required for selective preparations of high-quality target nanoarchitectures. This review summarizes various on-surface linking strategies for terminal alkynes, including non-bonding interactions as well as organometallic and covalent bonds, and presents examples to show effective control of surface assemblies and reactions of terminal alkynes by variations of the precursor structures, substrates and activation modes. Systematic studies of the on-surface linkage of terminal alkynes may help efficient and predictable preparations of surface nanomaterials and further understanding of surface chemistry.
文摘Reaction of perfluoroalkyl iodides with a series of alkynes under sulfinatodehalogenation condition gave a mixture of E/Z adducts very readily in high yield, thus constituted a mild, convenient and effective new method for the addition of perfluoroalkyl iodides to alkynes. Under the same con- dition, in the presence of 1-hexyne perfluoroalkyl bromide and 1,1,1-trichlorotrifluoroethane reacted only to give sulfinates as the major products. A radical mechanism was proposed for the addition reaction.
基金We thank the National Natural Science Foundation of China (Project 20462002) Natural Science Foundation of Jiangxi Province (Project 0420015) for financial support.
文摘(E)-α-Iodovinyl sulfides 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol % of Pd(PPh3)4 and 10 mol % of CuI to afford the corresponding 1, 3-enynylsulfides 3 stereospecifically in high yields.
基金the National Natural Science Foundation of China(No.20462002)Natural Science Foundation of Jiangxi Province(No.0420015)for financial support.
文摘(E)-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically afford the corresponding (Z)-2-sulfonyl-substituted 1,3-enynes 3 in high yields.
基金the National Natural Science Foundation of China (No.20372020) for financial support.
文摘The mixture of cesium hydroxide and terminal alkynes in dry DMF in the presence of 4 A molecular sieves was stirred for 3.0 h at room temperature under N2, then aryltellurenyl bromide in THF was added, and the reaction mixture was stirred for 2.0 h. Alkynyl tellurides were obtained in about 90% yields by flash chromatography.
文摘The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and Au)catalysis has emerged as a synthetic strategy for a wide range of organic chemical reactions in past decades.In coinage-metal-catalyzed carboxylation,CO_(2)is adopted as a carboxylation reagent,while coinage-metal salts,complexes,and nanoparticles(NPs)serve as a Lewis acid catalyst to activate unsaturated chemicals,particularly alkynes.This mini-review focuses on the recent advances of coinage-metal-catalyzed carboxylation of terminal alkynes with CO_(2).Other respects,such as the role of bases,the influence of trace water,and solvent effects are also highlighted.
基金supported financially by the National Natural Science Foundation of China(Project 51976225).
文摘Although precious transition metals such as palladium,platinum,and iridium are widely used in hydrogenation reactions,the earth-abundant transition metal-catalyzed highly selective semi-hydrogenation of terminal alkynes to terminal alkenes remains poorly developed and a challenge.Herein we demonstrate the excellent selective,cost-effective semi-hydrogenation of terminal alkynes via a novel graphene encapsulated Ni@N/C catalyst.The graphene layer encapsulated nano-catalyst Ni@N/C could significantly avoid metal leaching and improve the stability of the catalyst.The strong interaction of nitrogen with the Ni nanoparticles regulates the activity of Ni towards selective semi-hydrogenation of terminal alkynes.Substrates having un-functionalized as well as functionalized substituents,and substrates having sensitive functional groups(olefins,ketones)which pose a challenge to hydrogenate,were semi-hydrogenated with excellent conversion(up to 99%)and selectivity(up to 99%)under optimized reaction conditions.
基金This work was supported financially by the National Natural Science Foundation of China (Nos. 20972110 and 21002068).
文摘A facile and direct fluorination process of alkynes and diynes was developed, in the presence of n-butyllithium, the reaction of a series of terminal alkynes and diynes with the electrophilic fluorinating reagent (NFSI) proceeded to afford various 1-fluoroalkynes and 1-fluoro-l,3-diynes in moderate to high yields.
文摘A Sonogashira coupling reaction of aromatic halides with terminal alkynes in the presence of palladium powder, potassium fluoride, cuprous iodide and triphenylphosphine in methanol, giving the corresponding coupling products aryl alkynes in good to excellent yields, was investigated.