Internal alkynes are widespread skeletons in bioactive molecules and materials which are also used as important building blocks in chemical synthesis. Herein, we report a novel and efficient copper-catalyzed Sonogashi...Internal alkynes are widespread skeletons in bioactive molecules and materials which are also used as important building blocks in chemical synthesis. Herein, we report a novel and efficient copper-catalyzed Sonogashira reaction between sulfonium salts and alkynes through an anti-Markovnikov ring-opening pathway promoted by visible light. The coexistence of the nitrogen and phosphorus ligands in the system is the key to the success of this reaction. This radical type ring-opening reaction affords a new strategy for the synthesis of internal alkynes. Furthermore, this study is also an effective complement to the diverse reaction patterns of sulfonium salts.展开更多
An atom economicβ-C(sp^(3))−H chlorination of amide derivatives has been developed.This mild protocol employs CuCl_(2) instead of palladium catalysts with atom-economic HCl as chlorine sources and enables the late-st...An atom economicβ-C(sp^(3))−H chlorination of amide derivatives has been developed.This mild protocol employs CuCl_(2) instead of palladium catalysts with atom-economic HCl as chlorine sources and enables the late-stage functionalization of medicine derivatives.Mechanism studies suggest a plausible visible light triggered ligand-to-metal charge transfer(LMCT)/1,4-hydrogen atom transfer(HAT)cascade.展开更多
Herein,we disclose a novel copper-catalyzed C(sp)-H aryl amination of terminal alkynes with anthranils,enabling the rapid generation of highly reactive secondary N-aryl ynamines for the modular synthesis of structural...Herein,we disclose a novel copper-catalyzed C(sp)-H aryl amination of terminal alkynes with anthranils,enabling the rapid generation of highly reactive secondary N-aryl ynamines for the modular synthesis of structurally diverse C2-substituted quinolines and 2-quinolinones.The in-situ formed carbonyl-ynamines are prone to tautomerize to carbonyl-ketenimines,which can efficiently react with a series of nucleophiles,including amines,alcohols,phenols,thiols,thiophenols,active-methylene compounds,and even water to produce various quinoline derivatives with the generation of H_(2)O as a sole and green byproduct.This method also unlocks a practical route to create various quinoline-fused heterocycles and can be successfully applied to the late-stage modification of complex molecules and the concise synthesis of bioactive targets.Mechanistic studies reveal a coppercatalyzed inner-sphere nitrene transfer process by using anthranils as novel aryl nitrene precursors.展开更多
A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were syn...A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions.Notably,this protocol enables the integration of lactone fragments with many amine drugs and drug fragments.展开更多
We report a copper-catalyzed ligand-controlled selective carbonylative borofunctionalization ofα-substituted styrenes.This reaction provides a general and versatile procedure to synthesize a variety of synthetically ...We report a copper-catalyzed ligand-controlled selective carbonylative borofunctionalization ofα-substituted styrenes.This reaction provides a general and versatile procedure to synthesize a variety of synthetically usefulβ-boryl quaternary aldehydes and cyclopropyl boronate esters bearing a quaternary carbon center.With NHC(IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)as the ligand,the carbene intermediate reacts with O-H bond of alcohol while the carbene intermediate would undergo C-H bond insertion when using phosphine ligand[1,2-bis(diphenylphospino)ethane]as the ligand.Formation of a carbene intermediate has been proposed as the key step for this transformation.展开更多
Alkynes are one of the most significant functional groups in organic chemistry and great efforts have been made to explore efficient approach for the construction of chiral alkynes.The asymmetric C(sp^(3))–C(sp)cross...Alkynes are one of the most significant functional groups in organic chemistry and great efforts have been made to explore efficient approach for the construction of chiral alkynes.The asymmetric C(sp^(3))–C(sp)cross-coupling provides a significant complementary strategy through radical-initiated process.However,the stereocontrol of highly reactive and unstable radical intermediate has been a challenge for decades.To address this problem,a variety of chiral ligands are developed for initiating the reaction and achieving enantiocontrol of alkyl radicals.This review summarizes recent developments in copper-catalyzed enantioselective alkynylation of prochiral alkyl radicals and their brief mechanistic studies.展开更多
Chemical vapor deposition(CVD)using gaseous hydrocarbon sources has shown great promise for large-scale graphene growth,but high growth temperatures(typically 1000℃)require sophisticated and expensive equipment,which...Chemical vapor deposition(CVD)using gaseous hydrocarbon sources has shown great promise for large-scale graphene growth,but high growth temperatures(typically 1000℃)require sophisticated and expensive equipment,which increases graphene production costs.Here,we demonstrate a new approach to produce graphene at low cost from scrap steel sheets treated by thermal evaporation of copper plating,which is a derivative of traditional CVD technology.Without additional carbon sources,graphene film was successfully prepared on copper-coated scrap steel sheets at 820℃.The resulting graphene has few defects and uniform morphology,comparable to CVD graphene grown at 1000℃.Finally,the obtained graphene film is used in combination with an interdigital electrode to detect NO_(2)successfully,showing excellent performance.This technology expands the application of graphene in the manufacture of gas sensing devices and is compatible with traditional microelectronics technology.展开更多
Borylation of 1,3-enynes with bis(boronate)compounds often ends up with the formation of hydroborylated products,leaving the diborylation of 1,3-enynes for the formation of 1,4-diborylated allenes to be challenging.He...Borylation of 1,3-enynes with bis(boronate)compounds often ends up with the formation of hydroborylated products,leaving the diborylation of 1,3-enynes for the formation of 1,4-diborylated allenes to be challenging.Herein,a copper-catalyzed chemo-,regio-,and stereo-selective diborylation of 1,3-enynes for the efficient construction of 1,4-diborylated allenes under base-free conditions was reported.A wide range of 1,3-enynes bearing various functional groups can participant in the reaction and afforded the corresponding 1,4-diborylated allenes in good to excellent yields,which was enabled by the protocol of Bpin to BF3K conversion.the borylcopper species was supposed to selectively attack the C-C triple bond of the 1,3-enynes.展开更多
β-Chiral sulfones are structural motifs widely found in natural products and bioactive molecules, while also serving as important intermediates for the synthesis of valuable chiral scaffolds. In contrast to the rapid...β-Chiral sulfones are structural motifs widely found in natural products and bioactive molecules, while also serving as important intermediates for the synthesis of valuable chiral scaffolds. In contrast to the rapid growth of sulfur dioxide insertion chemistry over the last decade, enantioselective catalytic variants for accessing β-chiral sulfones, especially those bearing a quaternary carbon stereocenter, remain rare. Herein, we report an enantioselective copper/bisoxazoline catalyzed oxysulfonylation of alkenes to yield isoxazolinyl-containing β-chiral sulfones bearing quaternary carbon stereocenters with moderate to excellent yields and up to 96:4 er. The advantage and irreplaceability of this sulfur dioxide insertion catalytic system have been demonstrated by achieving transformations clearly unavailable with the previously reported sulfonyl chloride system. Additionally,the recoverability of the new-developed bisoxazoline ligand L9 and its reusability without any erosion of the catalytic activity and enantioselectivity further demonstrate the usefulness of the protocol.展开更多
The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radical precursors under mild conditions,which enables easy access to chiral 2,3-diaryl...The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radical precursors under mild conditions,which enables easy access to chiral 2,3-diaryl propionitriles with moderate to good enantiose-lectivities.This operationally straightforward reaction exhibits broad substrate scope and functional group tolerance.Notably,this method has been applied to the synthesis of chiral AlEgen as well as estrogen receptor-B agonist(R)-diarylpropionitrile(DPN).展开更多
The hydrosulfonylation of terminal alkynes employing sulfonohydrazides has been accomplished with cop- per-catalysis in the presence of BPO (benzoic peroxyanhydride). Generally, excellent yield of the vinyl sulfone ...The hydrosulfonylation of terminal alkynes employing sulfonohydrazides has been accomplished with cop- per-catalysis in the presence of BPO (benzoic peroxyanhydride). Generally, excellent yield of the vinyl sulfone products has been acquired by heating the reaction at 70℃ in DMSO.展开更多
A copper-catalyzed aerobic oxidative ring expansion reaction of isatins with 1,2,3,4-tetrahydroisoquinoline for the synthesis of tetra-cyclic quinazolinones has been developed.This reaction is performed smoothly under...A copper-catalyzed aerobic oxidative ring expansion reaction of isatins with 1,2,3,4-tetrahydroisoquinoline for the synthesis of tetra-cyclic quinazolinones has been developed.This reaction is performed smoothly under simple conditions to give the corresponding products in moderate to good yields with good functional group tolerance.展开更多
Henry reaction is one of the most classical reactions to construct synthetically useful product nitro alcohol, which as a privileged skeleton is widely distributed in various pharmaceuticals. This review summarizes th...Henry reaction is one of the most classical reactions to construct synthetically useful product nitro alcohol, which as a privileged skeleton is widely distributed in various pharmaceuticals. This review summarizes the recent progress of copper-catalyzed asymmetric Henry reaction from 2011 to 2016. The significant progress that has been made in this area will be highlighted and some of challenges that the author believes may be hindering further progress will be revealed.展开更多
Catalytic asymmetric aza-Michael represents one of the most convenient and atom-economical approaches for the rapid construction of biologically active chiralβ-amino acid frameworks.However,the direct enantioselectiv...Catalytic asymmetric aza-Michael represents one of the most convenient and atom-economical approaches for the rapid construction of biologically active chiralβ-amino acid frameworks.However,the direct enantioselective addition of nitrogen-based nucleophiles to intrinsically low reactivity ofα,β-unsaturated carboxylic acid,ester,and amide,as well as simpleα,β-unsaturated nitrile,remains a long-standing challenge.展开更多
Borylative cyclization of E-3-arylallyl carbamoyl chlorides is achieved through copper catalyzed intramolecular carboboration with B_(2)pin_(2).2-Aryl-3-boryl-γ-lactams are formed with exclusive cisdiastereoselectivi...Borylative cyclization of E-3-arylallyl carbamoyl chlorides is achieved through copper catalyzed intramolecular carboboration with B_(2)pin_(2).2-Aryl-3-boryl-γ-lactams are formed with exclusive cisdiastereoselectivity.CuBr-Dppp combination gives the best outcomes.The substrate scope is profiled.展开更多
A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of pr...A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of prefabricated arylselenation reagent and address the facile over-selention issues,but also enrich the chemistry of selenium powder.Importantly,this reaction could be extended to pyrrole,and the practical utility of this transformation has been demonstrated in gram-scale synthesis and late-stage indolylselenation of Clofibrate-derived propiolic acid.展开更多
Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Her...Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Herein, we disclosed a highly enantioselective propargylic substitution of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand. This strategy is amenable to a broad range of substrates, uses readily available starting materials, provides excellent yields with remarkable enantioselectivity under mild conditions, and enables attractive products diversification routes.展开更多
Copper-catalyzed divergent annulations betweenα-diketones and alkynylα-diketones have been achieved,delivering a series of highly functionalized and biologically important cis-hexahydro-2Hcyclopenta[b]furan(HCPF)and...Copper-catalyzed divergent annulations betweenα-diketones and alkynylα-diketones have been achieved,delivering a series of highly functionalized and biologically important cis-hexahydro-2Hcyclopenta[b]furan(HCPF)and 2-hydroxydihydrofuran-3(2H)-one(HDFO)products with high levels of stereoselectivity under identical conditions.The protocol features the use of earth-abundant copper catalyst,mild conditions,shortening synthetic routes in constructing different molecular frameworks,and reducing the corresponding possible waste production.The substituents of the nucleophilicα-diketones play crucial roles in switching the reaction pathways.展开更多
Main observation and conclusion Stereodefinedβ,γ-unsaturated carbony|compounds are important yet synthetically challenging units in natural products and drugs.Disclosed herein is a mild,rapid copper-catalyzed dibory...Main observation and conclusion Stereodefinedβ,γ-unsaturated carbony|compounds are important yet synthetically challenging units in natural products and drugs.Disclosed herein is a mild,rapid copper-catalyzed diborylation reaction of cross-conjugated enynones as a step-economic and modular approach to stereodefined multifunctionalizedβ,γ-unsaturated ketones by fine control of chemo-,regio-,Z/E and diastereoselectivity.The substrate scope was examined and a possible catalytic cycle was proposed to explain the multifaceted selectivity.展开更多
Since organoboron compounds readily undergo a diverse array of transformations and are widely used in various fields,the development of C-B-bondforming reactions have attracted considerable attention.Herein,we report ...Since organoboron compounds readily undergo a diverse array of transformations and are widely used in various fields,the development of C-B-bondforming reactions have attracted considerable attention.Herein,we report a new method for forming C-B bonds by means of Cu-catalyzed ring-opening/borylation reactions of cyclopropenes.This method provides efficient access to a new type of stable allylborane-Lewis base adduct,which is a versatile synthon.The configuration of the products can be well controlled with this method,and some of the configurations we obtained are inaccessible by other catalytic methods for generating allylborons.Mechanistic studies indicated that the reactions proceed via insertion of an alkenyl Cu carbene—generated in situ by cyclopropene ring opening—into the B-H bond;the ring-opening step determines both the rate and stereochemistry.展开更多
基金supported by the National Natural Science Foundation of China(22271170)the Scientific Research Foundation of Qingdao University of Science and Technology(1203043003457).
文摘Internal alkynes are widespread skeletons in bioactive molecules and materials which are also used as important building blocks in chemical synthesis. Herein, we report a novel and efficient copper-catalyzed Sonogashira reaction between sulfonium salts and alkynes through an anti-Markovnikov ring-opening pathway promoted by visible light. The coexistence of the nitrogen and phosphorus ligands in the system is the key to the success of this reaction. This radical type ring-opening reaction affords a new strategy for the synthesis of internal alkynes. Furthermore, this study is also an effective complement to the diverse reaction patterns of sulfonium salts.
基金support from the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(No.UNPYSCT-2017124).
文摘An atom economicβ-C(sp^(3))−H chlorination of amide derivatives has been developed.This mild protocol employs CuCl_(2) instead of palladium catalysts with atom-economic HCl as chlorine sources and enables the late-stage functionalization of medicine derivatives.Mechanism studies suggest a plausible visible light triggered ligand-to-metal charge transfer(LMCT)/1,4-hydrogen atom transfer(HAT)cascade.
基金supported by the National Natural Science Foundation of China (22271065,22271314)the Guangzhou Basic and Applied Research (202201010396)。
文摘Herein,we disclose a novel copper-catalyzed C(sp)-H aryl amination of terminal alkynes with anthranils,enabling the rapid generation of highly reactive secondary N-aryl ynamines for the modular synthesis of structurally diverse C2-substituted quinolines and 2-quinolinones.The in-situ formed carbonyl-ynamines are prone to tautomerize to carbonyl-ketenimines,which can efficiently react with a series of nucleophiles,including amines,alcohols,phenols,thiols,thiophenols,active-methylene compounds,and even water to produce various quinoline derivatives with the generation of H_(2)O as a sole and green byproduct.This method also unlocks a practical route to create various quinoline-fused heterocycles and can be successfully applied to the late-stage modification of complex molecules and the concise synthesis of bioactive targets.Mechanistic studies reveal a coppercatalyzed inner-sphere nitrene transfer process by using anthranils as novel aryl nitrene precursors.
基金Financial support from the National Natural Science Foundation of China(Nos.21971201,22171220)the Fundamental Research Funds of the Central Universities(No.xtr072022003)。
文摘A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions.Notably,this protocol enables the integration of lactone fragments with many amine drugs and drug fragments.
基金appreciate the financial support from DICP(Dalian Institute of Chemical Physics,CAS)and the K.C.Wong Education Foundation(grant no.GJTD-2020-08).
文摘We report a copper-catalyzed ligand-controlled selective carbonylative borofunctionalization ofα-substituted styrenes.This reaction provides a general and versatile procedure to synthesize a variety of synthetically usefulβ-boryl quaternary aldehydes and cyclopropyl boronate esters bearing a quaternary carbon center.With NHC(IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)as the ligand,the carbene intermediate reacts with O-H bond of alcohol while the carbene intermediate would undergo C-H bond insertion when using phosphine ligand[1,2-bis(diphenylphospino)ethane]as the ligand.Formation of a carbene intermediate has been proposed as the key step for this transformation.
基金We are grateful to the National Natural Science Foundation of China(22071073,22271112,21772218,and 21821002)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences and the Central China Normal University(CCNU).
文摘Alkynes are one of the most significant functional groups in organic chemistry and great efforts have been made to explore efficient approach for the construction of chiral alkynes.The asymmetric C(sp^(3))–C(sp)cross-coupling provides a significant complementary strategy through radical-initiated process.However,the stereocontrol of highly reactive and unstable radical intermediate has been a challenge for decades.To address this problem,a variety of chiral ligands are developed for initiating the reaction and achieving enantiocontrol of alkyl radicals.This review summarizes recent developments in copper-catalyzed enantioselective alkynylation of prochiral alkyl radicals and their brief mechanistic studies.
基金the National Natural Science Foundation of China(No.52073305)Natural Science Foundation of Shandong Province(No.ZR2020QE048)+1 种基金State Key Laboratory of Heavy Oil Processing(No.SKLHOP202101006)National Defense Science and Technology Innovation Special Zone Project(No.22-05-CXZX-04-04-29).
文摘Chemical vapor deposition(CVD)using gaseous hydrocarbon sources has shown great promise for large-scale graphene growth,but high growth temperatures(typically 1000℃)require sophisticated and expensive equipment,which increases graphene production costs.Here,we demonstrate a new approach to produce graphene at low cost from scrap steel sheets treated by thermal evaporation of copper plating,which is a derivative of traditional CVD technology.Without additional carbon sources,graphene film was successfully prepared on copper-coated scrap steel sheets at 820℃.The resulting graphene has few defects and uniform morphology,comparable to CVD graphene grown at 1000℃.Finally,the obtained graphene film is used in combination with an interdigital electrode to detect NO_(2)successfully,showing excellent performance.This technology expands the application of graphene in the manufacture of gas sensing devices and is compatible with traditional microelectronics technology.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22001251,21922112,and 22225107)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)+1 种基金National Key R&D Program of China(No.2017YFA0700103)the Guizhou Provincial S&T Project(No.2018[4007]).
文摘Borylation of 1,3-enynes with bis(boronate)compounds often ends up with the formation of hydroborylated products,leaving the diborylation of 1,3-enynes for the formation of 1,4-diborylated allenes to be challenging.Herein,a copper-catalyzed chemo-,regio-,and stereo-selective diborylation of 1,3-enynes for the efficient construction of 1,4-diborylated allenes under base-free conditions was reported.A wide range of 1,3-enynes bearing various functional groups can participant in the reaction and afforded the corresponding 1,4-diborylated allenes in good to excellent yields,which was enabled by the protocol of Bpin to BF3K conversion.the borylcopper species was supposed to selectively attack the C-C triple bond of the 1,3-enynes.
基金supported by the National Natural Science Foundation of China(22171206)the Natural Science Foundation of Zhejiang Province(Z23B020002,LY22B020003,)+1 种基金the Open Foundation of Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers(E22307)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(2020ZD04)。
文摘β-Chiral sulfones are structural motifs widely found in natural products and bioactive molecules, while also serving as important intermediates for the synthesis of valuable chiral scaffolds. In contrast to the rapid growth of sulfur dioxide insertion chemistry over the last decade, enantioselective catalytic variants for accessing β-chiral sulfones, especially those bearing a quaternary carbon stereocenter, remain rare. Herein, we report an enantioselective copper/bisoxazoline catalyzed oxysulfonylation of alkenes to yield isoxazolinyl-containing β-chiral sulfones bearing quaternary carbon stereocenters with moderate to excellent yields and up to 96:4 er. The advantage and irreplaceability of this sulfur dioxide insertion catalytic system have been demonstrated by achieving transformations clearly unavailable with the previously reported sulfonyl chloride system. Additionally,the recoverability of the new-developed bisoxazoline ligand L9 and its reusability without any erosion of the catalytic activity and enantioselectivity further demonstrate the usefulness of the protocol.
基金We are grateful for financial support from the National Nature Science Foundation of China(Nos.21532009,91956202,21821002 and 21790330)the Science and Technology Commission of Shanghai Municipality(Nos.20JC1417000,19590750400 and 17JC1401200)+2 种基金the strategic Priority Research Program(No.XDB20000000)the Key Research Program of Frontier Science(QYZDJSSWSLH055)the International Partnership Program(No.121731KY5B20190016)of the Chinese Academy of Sciences.
文摘The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radical precursors under mild conditions,which enables easy access to chiral 2,3-diaryl propionitriles with moderate to good enantiose-lectivities.This operationally straightforward reaction exhibits broad substrate scope and functional group tolerance.Notably,this method has been applied to the synthesis of chiral AlEgen as well as estrogen receptor-B agonist(R)-diarylpropionitrile(DPN).
基金This work is financially supported by the National Natural Science Foundation of China (No. 21562024).
文摘The hydrosulfonylation of terminal alkynes employing sulfonohydrazides has been accomplished with cop- per-catalysis in the presence of BPO (benzoic peroxyanhydride). Generally, excellent yield of the vinyl sulfone products has been acquired by heating the reaction at 70℃ in DMSO.
基金This work was supported by the National Natural Science Foundation of China(21871226,21502160 and 21572194)Scien-tific Research Fund of Hunan Provincial Education Department(19B564)+2 种基金Hunan Provincial Natural Science Foundation of China(2020113032)Efficient Resource Uilization,the China Postdoc-toral Science Foundation(2018M632976 and 2019T120709)Scientific Research Fund of Xiangtan University(XDCX2020B110).
文摘A copper-catalyzed aerobic oxidative ring expansion reaction of isatins with 1,2,3,4-tetrahydroisoquinoline for the synthesis of tetra-cyclic quinazolinones has been developed.This reaction is performed smoothly under simple conditions to give the corresponding products in moderate to good yields with good functional group tolerance.
基金the National Natural Science Foundation of China (Nos. 2127222, 21432009, 21472177, J1310010)Chinese Academy of Sciences(No. XDB20000000)
文摘Henry reaction is one of the most classical reactions to construct synthetically useful product nitro alcohol, which as a privileged skeleton is widely distributed in various pharmaceuticals. This review summarizes the recent progress of copper-catalyzed asymmetric Henry reaction from 2011 to 2016. The significant progress that has been made in this area will be highlighted and some of challenges that the author believes may be hindering further progress will be revealed.
基金the National Natural Science Foundation of China(grant nos.21672033,21801039,and 21831002)the Jilin Educational Committee(grant no.JJKH20190269KJ)the Fundamental Research Funds for the Central Universities,and the Ten Thousand Talents Program for generous financial support.
文摘Catalytic asymmetric aza-Michael represents one of the most convenient and atom-economical approaches for the rapid construction of biologically active chiralβ-amino acid frameworks.However,the direct enantioselective addition of nitrogen-based nucleophiles to intrinsically low reactivity ofα,β-unsaturated carboxylic acid,ester,and amide,as well as simpleα,β-unsaturated nitrile,remains a long-standing challenge.
基金the National Natural Science Foundation of China(No.21672027)for financial supportsupported by High-Level Entrepreneurial Talent Team of Jiangsu Province(No.2017-37)。
文摘Borylative cyclization of E-3-arylallyl carbamoyl chlorides is achieved through copper catalyzed intramolecular carboboration with B_(2)pin_(2).2-Aryl-3-boryl-γ-lactams are formed with exclusive cisdiastereoselectivity.CuBr-Dppp combination gives the best outcomes.The substrate scope is profiled.
基金Financial support from the National Natural Science Foundation of China(Nos.81803484,21602158)Zhejiang Provincial Natural Science Foundation(No.LY19B020011)Public Welfare Science and Technology Project of Wenzhou(Nos.Y20190132,Y20180233)are greatly appreciated.
文摘A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of prefabricated arylselenation reagent and address the facile over-selention issues,but also enrich the chemistry of selenium powder.Importantly,this reaction could be extended to pyrrole,and the practical utility of this transformation has been demonstrated in gram-scale synthesis and late-stage indolylselenation of Clofibrate-derived propiolic acid.
基金financial support from the National Natural Science Foundation of China (No.21801087)Fundamental Research Funds for the Central Universities CCNU (No.CCNU19QN064)+2 种基金the Ministry of Science and Technology of China (No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists (No.GZS2020001)the Key Scientific and Technological Project of Henan Province (No.212102311068)。
文摘Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Herein, we disclosed a highly enantioselective propargylic substitution of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand. This strategy is amenable to a broad range of substrates, uses readily available starting materials, provides excellent yields with remarkable enantioselectivity under mild conditions, and enables attractive products diversification routes.
基金the National Natural Science Foundation of China(Nos.22071242 and 21871260)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)+1 种基金Fujian Natural Science Foundation(No.2018J05035)Science and Technology Research Program of the Education Department of Jiangxi Province(No.GJJ1991151)。
文摘Copper-catalyzed divergent annulations betweenα-diketones and alkynylα-diketones have been achieved,delivering a series of highly functionalized and biologically important cis-hexahydro-2Hcyclopenta[b]furan(HCPF)and 2-hydroxydihydrofuran-3(2H)-one(HDFO)products with high levels of stereoselectivity under identical conditions.The protocol features the use of earth-abundant copper catalyst,mild conditions,shortening synthetic routes in constructing different molecular frameworks,and reducing the corresponding possible waste production.The substituents of the nucleophilicα-diketones play crucial roles in switching the reaction pathways.
基金the National Natural Sci-ence Foundation of China(Nos.21672168,21971202)the Key Laboratory Construction Program of Xi'an Municipal Bureau of Science and Technology(No.201805056ZD7CG40)。
文摘Main observation and conclusion Stereodefinedβ,γ-unsaturated carbony|compounds are important yet synthetically challenging units in natural products and drugs.Disclosed herein is a mild,rapid copper-catalyzed diborylation reaction of cross-conjugated enynones as a step-economic and modular approach to stereodefined multifunctionalizedβ,γ-unsaturated ketones by fine control of chemo-,regio-,Z/E and diastereoselectivity.The substrate scope was examined and a possible catalytic cycle was proposed to explain the multifaceted selectivity.
基金the National Natural Science Foundation of China(nos.21625204 and 21971119)the“111”project(B06005)of the Ministry of Education of China+1 种基金National Program for Support of Top-notch Young ProfessionalsKey-Area Research and Development Program of Guangdong Province(no.2020B010188001)for financial support.
文摘Since organoboron compounds readily undergo a diverse array of transformations and are widely used in various fields,the development of C-B-bondforming reactions have attracted considerable attention.Herein,we report a new method for forming C-B bonds by means of Cu-catalyzed ring-opening/borylation reactions of cyclopropenes.This method provides efficient access to a new type of stable allylborane-Lewis base adduct,which is a versatile synthon.The configuration of the products can be well controlled with this method,and some of the configurations we obtained are inaccessible by other catalytic methods for generating allylborons.Mechanistic studies indicated that the reactions proceed via insertion of an alkenyl Cu carbene—generated in situ by cyclopropene ring opening—into the B-H bond;the ring-opening step determines both the rate and stereochemistry.