近日,我校化学化工学院江智勇教授团队在国际化学顶级期刊Nature Chemistry上发表了题为"Leveraging Electron Donor-Acceptor Complexes for Kinetic Resolution in Catalytic Asymmetric Photochemical Synthesis”的研究论文....近日,我校化学化工学院江智勇教授团队在国际化学顶级期刊Nature Chemistry上发表了题为"Leveraging Electron Donor-Acceptor Complexes for Kinetic Resolution in Catalytic Asymmetric Photochemical Synthesis”的研究论文.该研究首次提出了一种基于电子供体-受体(EDA)复合物的动力学拆分策略,成功实现了催化不对称光化学合成.化学化工学院青年教师邵天举博士为论文第一作者,我校学术副校长、化学化工学院院长江智勇教授为唯一通讯作者,河南师范大学为第一通讯单位.展开更多
Chiral benzylic amines are important motifs in medicines.A dicationic nickel complex of chiral diphosphine(R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using iso...Chiral benzylic amines are important motifs in medicines.A dicationic nickel complex of chiral diphosphine(R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using isopropanol as hydrogen source.The reaction is easily scaled up in a gram-scale synthesis using 1 mol% nickel catalyst and it is applied to an asymmetric synthesis of(S)-rivastigmine.Building on this success,we achieved rare examples of asymmetric hydrogen borrowing reactions with arylamines using an Earth-abundant 3d metal,nickel.展开更多
Catalytic reduction reactions using isopropanol(IPA)as a transfer hydrogenating agent are gaining significant attention due to the low cost and large-scale production of IPA.Traditional methods for carbon-carbon(C—C)...Catalytic reduction reactions using isopropanol(IPA)as a transfer hydrogenating agent are gaining significant attention due to the low cost and large-scale production of IPA.Traditional methods for carbon-carbon(C—C)bond construction often rely on expensive and scarce transition metal catalysts,raising concerns about sustainability and environmental impact.To address these challenges,we develop a bifunctional photocatalyst,phloroglucinol carbon quantum dot(PG-CQD).It facilitates catalytic transfer hydrogenation(CTH)with IPA as the hydrogen donor.PG-CQDs exhibit both dehydrogenation and reduction activities,enabling the formation of vicinal diols under mild conditions with visible light irradiation.We propose a CTH mechanism that has been successfully validated through experiments.The catalytic system demonstrates remarkable versatility,enabling the synthesis of various vicinal diols from diverseα-keto ester substrates with good or excellent yields.These findings offer a sustainable synthetic strategy that aligns with green chemistry principles and establish a promising pathway for the development of environmentally benign and energy-efficient organic transformations.展开更多
By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones,the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bo...By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones,the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner.In addition,the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.展开更多
The highly selective C(sp^(3))-H bond activation strategy will greatly promote the efficient utilization of natural hydrocarbon resources.In the past few decades,chemists have developed effective methods to activate t...The highly selective C(sp^(3))-H bond activation strategy will greatly promote the efficient utilization of natural hydrocarbon resources.In the past few decades,chemists have developed effective methods to activate the 1°C-H bonds with the smallest steric hindrance and the 3°C-H bonds with the largest steric hindrance in alkanes.However,there is currently no effective strategy for activating the 2°C-H bond with steric hindrance between the two.Here,we combine electrochemistry and organic catalysis to report a highly selective method for the chlorination of alkane 2°C-H bonds.By adjusting the specific cavity size of the organic molecule catalyst to precisely undergo hydrogen atom transfer with the secondary C-H bond,the corresponding carbon-centered free radicals are generated,which then combine with chlorine atoms to produce chlorinated alkanes at specific sites.In addition,the use of inexpensive and easily reusable graphite felt electrodes and simple electrochemical conditions makes it easy to scale up the system to kilogram-level production.展开更多
In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mi...In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mild conditions.Various substituted benzylamines containing diverse functional groups and even highly reactive moieties,such as cyano,amide and alkene groups could be successfully transformed to the carboxylated products.Notably,this method proved to be applicable to the late-stage modification of biorelevant compounds,highlighting its potential for synthetic chemistry.Mechanistic studies such as radical trapping experiments,kinetic isotope effect(KIE) tests and cyclic voltammetry(CV) studies provided useful insight into this transformation.展开更多
Herein,we report a novel,visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides...Herein,we report a novel,visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides as alkyl radical precursors.This strategy leverages Eosin Y as a photocatalyst in a defluorinative alkylation reaction and a catalyst-free electron donor-acceptor(EDA)complex-mediated hydroalkylation process.By modulating the reaction conditions,the desired products were selectively obtained with excellent chemo-selectivity and in high yields.The protocol accommodates a wide variety of substrates,including primary,secondary,and tertiary alcohols,as well as diverse α-trifluoromethyl styrenes,and is applicable to late-stage functionalization of natural products and bioactive molecules.展开更多
The radical addition/functional group migration strategy has emerged as a powerful tool for the difunctionalization of unsaturated hydrocarbons,yet the heteroatom-mediated functional group migration remains largely un...The radical addition/functional group migration strategy has emerged as a powerful tool for the difunctionalization of unsaturated hydrocarbons,yet the heteroatom-mediated functional group migration remains largely unexplored.Herein,we report an unprecedented radical difunctionalization of alkynes employing oxime esters as bifunctional reagents through a novel C-centered radical addition/N-centered radical translocation sequence.This innovative transformation paradigm enables efficient alkylamination of alkynes under mild photocatalytic redox conditions.Mechanistic investigations reveal a cascade sequence initiated by single-electron transfer from oxime derivatives,proceeding through radical addition,6-exo-trig cyclization,and subsequent imino group migration.展开更多
Fluorinated motifs are prevalent in both pharmaceuticals and agrochemicals.The incorporation of fluorine-containing moieties to drug candidates has emerged as a potent strategy for lead optimization in pharmaceutical ...Fluorinated motifs are prevalent in both pharmaceuticals and agrochemicals.The incorporation of fluorine-containing moieties to drug candidates has emerged as a potent strategy for lead optimization in pharmaceutical research and development.While extensive research has been devoted to constructing molecules that incorporate a trifluoromethylthio(SCF_(3)−)group on a stereogenic carbon,the synthesis of trifluoromethylthiolated alkanes featuring a SCF_(3)-substituted stereogenic carbon at non-activated site remains understudied.Herein,we report a Cu-catalyzed regio-and enantioselective hydroallylation of 1-trifluoromethylthiolated alkenes.Important to the process is the regio-and enantioselective Cu-H insertion to SCF_(3)-substituted alkene to form chiralα-SCF_(3) alkyl copper intermediates,outcompeting unproductive insertion to the coupling partner,and eventually proceed to afford optically active homoallylic trifluoromethylthiolated products.展开更多
Radical cycloaddition reactions(RCRs) are highly effective methods for constructing complex carbo-and heterocycles,which are frequently encountered in natural products that exhibit intriguing biological properties and...Radical cycloaddition reactions(RCRs) are highly effective methods for constructing complex carbo-and heterocycles,which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry.Radical-mediated cycloaddition strategies,which recycle radical character,are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy.This review focuses on recent developments and synthetic applications in RCRs,with an emphasis on visible lightinduced radical photocycloaddition reactions(RPCRs),transition metal-catalyzed approaches,and small molecule-catalyzed methods.By highlighting some outstanding innovations and addressing current challenges,this review aims to identify potential areas for improvement.These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.展开更多
Albeit notable endeavors in the construction of organophosphorodithioates,the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge.Herein,an efficient orga...Albeit notable endeavors in the construction of organophosphorodithioates,the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge.Herein,an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine.This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields(up to 98 %yield) with high stereoselectivities(up to 97 % ee and >99:1 E/Z).展开更多
Sulfoxides and sulfide compounds have broad-spectrum biological properties and have received considerable attention in the past few decades.Herein we reported two metal and oxidant-free,practical and efficient methods...Sulfoxides and sulfide compounds have broad-spectrum biological properties and have received considerable attention in the past few decades.Herein we reported two metal and oxidant-free,practical and efficient methods for the synthesis of highly synthetically useful and structurally diverse ortho-aminoaryl sulfoxides and 3,4,5-trisubstituted oxazolones from readily accessible N-arylhydroxylamines and N-thiophthalimides.This rapid transformation occurred smoothly to achieve chemo-and regioselective cascade rearrangements due to the differences of the protecting-groups of the nitrogen atom of N-arylhydroxyamines.DFT studies suggested that the competing S-O and S-C bond formations via SN2 nucleophilic substitution are crucial for the observed protecting-group-dependent chemoselectivity.Subsequent applications have shown that these two protocols might be powerful tools for the construction of sulfur-containing complex molecules under simple conditions.展开更多
Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable ...Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds.In comparison with traditional thermal or metal-mediated carbene transfer reactions,visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules.Recently,visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation,mild condition,high atom economy and rich structural diversity.This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles.The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review.The future research direction and challenges in this area are also discussed.展开更多
The carbonylation of amines offers a promising route for synthesizing N-substituted carbamates with high atom economy.However,conventional catalysts exhibit limited catalytic efficiency,and the underlying proton trans...The carbonylation of amines offers a promising route for synthesizing N-substituted carbamates with high atom economy.However,conventional catalysts exhibit limited catalytic efficiency,and the underlying proton transfer mechanism remains elusive.Herein,we reported a metal-free,room-temperature strategy utilizing 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)as a dual hydrogen bond catalyst to synergistically activate propylamine(PA)and dimethyl carbonate(DMC).This green catalytic system achieves a 10-fold acceleration in reaction rate compared to other hydrogen bonding catalysts under mild conditions.This is enabled by dual hydrogen bonding of TBD with PA and DMC,which facilitates rapid proton transfer and stabilizes tetrahedral intermediates.Theoretical calculations confirm that the dual hydrogen bond system significantly lowers activation energy compared to single hydrogen bond analogs.Furthermore,it was revealed that the hydrogen bonding network within the product is the primary factor responsible for the sluggish reaction rate.This study demonstrates the effectiveness of a dual hydrogen bond system in accelerating the carbonylation of amines and provides a green route to access carbamates.展开更多
文摘近日,我校化学化工学院江智勇教授团队在国际化学顶级期刊Nature Chemistry上发表了题为"Leveraging Electron Donor-Acceptor Complexes for Kinetic Resolution in Catalytic Asymmetric Photochemical Synthesis”的研究论文.该研究首次提出了一种基于电子供体-受体(EDA)复合物的动力学拆分策略,成功实现了催化不对称光化学合成.化学化工学院青年教师邵天举博士为论文第一作者,我校学术副校长、化学化工学院院长江智勇教授为唯一通讯作者,河南师范大学为第一通讯单位.
基金supported by the National Natural Science Foundation of China(Nos.22271007,W2431014)Peking University Shenzhen Graduate School+2 种基金State Key Laboratory of Chemical OncogenomicsShenzhen Key Laboratory of Chemical GenomicsShenzhen Bay Laboratory.
文摘Chiral benzylic amines are important motifs in medicines.A dicationic nickel complex of chiral diphosphine(R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using isopropanol as hydrogen source.The reaction is easily scaled up in a gram-scale synthesis using 1 mol% nickel catalyst and it is applied to an asymmetric synthesis of(S)-rivastigmine.Building on this success,we achieved rare examples of asymmetric hydrogen borrowing reactions with arylamines using an Earth-abundant 3d metal,nickel.
基金National Natural Science Foundation of China(Nos.21902023 and 21901252)Shanghai Pujiang Program,China(No.19PJ1400300)+1 种基金Professor of Special Appointment(Eastern Scholar),ChinaShanghai Institutions of Higher Education Fundamental Research Funds for the Central Universities,China(No.0900000155)。
文摘Catalytic reduction reactions using isopropanol(IPA)as a transfer hydrogenating agent are gaining significant attention due to the low cost and large-scale production of IPA.Traditional methods for carbon-carbon(C—C)bond construction often rely on expensive and scarce transition metal catalysts,raising concerns about sustainability and environmental impact.To address these challenges,we develop a bifunctional photocatalyst,phloroglucinol carbon quantum dot(PG-CQD).It facilitates catalytic transfer hydrogenation(CTH)with IPA as the hydrogen donor.PG-CQDs exhibit both dehydrogenation and reduction activities,enabling the formation of vicinal diols under mild conditions with visible light irradiation.We propose a CTH mechanism that has been successfully validated through experiments.The catalytic system demonstrates remarkable versatility,enabling the synthesis of various vicinal diols from diverseα-keto ester substrates with good or excellent yields.These findings offer a sustainable synthetic strategy that aligns with green chemistry principles and establish a promising pathway for the development of environmentally benign and energy-efficient organic transformations.
基金financially supported by the National Natural Science Foundation of China (No.22261026)。
文摘By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones,the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner.In addition,the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.
基金supported by the National Natural Science Foundation of China(22371129)the First Class Discipline of Traditional Chinese Medicine“Leading Plan”Scientific Research Special Project of Nanjing University of Chinese Medicine(ZYXPY2024-005)。
文摘The highly selective C(sp^(3))-H bond activation strategy will greatly promote the efficient utilization of natural hydrocarbon resources.In the past few decades,chemists have developed effective methods to activate the 1°C-H bonds with the smallest steric hindrance and the 3°C-H bonds with the largest steric hindrance in alkanes.However,there is currently no effective strategy for activating the 2°C-H bond with steric hindrance between the two.Here,we combine electrochemistry and organic catalysis to report a highly selective method for the chlorination of alkane 2°C-H bonds.By adjusting the specific cavity size of the organic molecule catalyst to precisely undergo hydrogen atom transfer with the secondary C-H bond,the corresponding carbon-centered free radicals are generated,which then combine with chlorine atoms to produce chlorinated alkanes at specific sites.In addition,the use of inexpensive and easily reusable graphite felt electrodes and simple electrochemical conditions makes it easy to scale up the system to kilogram-level production.
基金Financial support from National Key R&D Program of China (No.2023YFA1507203)National Natural Science Foundation of China (Nos.22371149 and 22188101)+3 种基金the Fundamental Research Funds for the Central Universities (No.63224098)Frontiers Science Center for New Organic Matter,Nankai University (No.63181206)Nankai University are gratefully acknowledgedthe Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mild conditions.Various substituted benzylamines containing diverse functional groups and even highly reactive moieties,such as cyano,amide and alkene groups could be successfully transformed to the carboxylated products.Notably,this method proved to be applicable to the late-stage modification of biorelevant compounds,highlighting its potential for synthetic chemistry.Mechanistic studies such as radical trapping experiments,kinetic isotope effect(KIE) tests and cyclic voltammetry(CV) studies provided useful insight into this transformation.
基金supported by the National Natural Science Foundation of China(22401151)the Basic Research Program of Jiangsu Province(BK20220408)+1 种基金the Innovation and Entrepreneurship Team of Jiangsu Province(JSSCTD202345)the Specially Appointed Professor Plan of Jiangsu Province。
文摘Herein,we report a novel,visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides as alkyl radical precursors.This strategy leverages Eosin Y as a photocatalyst in a defluorinative alkylation reaction and a catalyst-free electron donor-acceptor(EDA)complex-mediated hydroalkylation process.By modulating the reaction conditions,the desired products were selectively obtained with excellent chemo-selectivity and in high yields.The protocol accommodates a wide variety of substrates,including primary,secondary,and tertiary alcohols,as well as diverse α-trifluoromethyl styrenes,and is applicable to late-stage functionalization of natural products and bioactive molecules.
基金supported by the Shaanxi Provincial Natural Science Basic Research Plan(2025JC-YBMS-114)the National Key Research and Development Program of China(2024YFB3212500)+1 种基金the Xi’an Jiaotong University(7121192002)the Fundamental Research Funds for the Central Universities(xzy022024023)。
文摘The radical addition/functional group migration strategy has emerged as a powerful tool for the difunctionalization of unsaturated hydrocarbons,yet the heteroatom-mediated functional group migration remains largely unexplored.Herein,we report an unprecedented radical difunctionalization of alkynes employing oxime esters as bifunctional reagents through a novel C-centered radical addition/N-centered radical translocation sequence.This innovative transformation paradigm enables efficient alkylamination of alkynes under mild photocatalytic redox conditions.Mechanistic investigations reveal a cascade sequence initiated by single-electron transfer from oxime derivatives,proceeding through radical addition,6-exo-trig cyclization,and subsequent imino group migration.
基金the National Key R&D Program of China(No.2021YFF0701700)the National Natural Science Foundation of China(Nos.22271264 and 21971228)for financial support.
文摘Fluorinated motifs are prevalent in both pharmaceuticals and agrochemicals.The incorporation of fluorine-containing moieties to drug candidates has emerged as a potent strategy for lead optimization in pharmaceutical research and development.While extensive research has been devoted to constructing molecules that incorporate a trifluoromethylthio(SCF_(3)−)group on a stereogenic carbon,the synthesis of trifluoromethylthiolated alkanes featuring a SCF_(3)-substituted stereogenic carbon at non-activated site remains understudied.Herein,we report a Cu-catalyzed regio-and enantioselective hydroallylation of 1-trifluoromethylthiolated alkenes.Important to the process is the regio-and enantioselective Cu-H insertion to SCF_(3)-substituted alkene to form chiralα-SCF_(3) alkyl copper intermediates,outcompeting unproductive insertion to the coupling partner,and eventually proceed to afford optically active homoallylic trifluoromethylthiolated products.
基金The financial support from the National Natural Science Foundation of China (Nos.22150410339,W2432012,22301237 and 22171218)the Ministry of Science and Technology China (No.wgxz2022188) is greatly acknowledged。
文摘Radical cycloaddition reactions(RCRs) are highly effective methods for constructing complex carbo-and heterocycles,which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry.Radical-mediated cycloaddition strategies,which recycle radical character,are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy.This review focuses on recent developments and synthetic applications in RCRs,with an emphasis on visible lightinduced radical photocycloaddition reactions(RPCRs),transition metal-catalyzed approaches,and small molecule-catalyzed methods.By highlighting some outstanding innovations and addressing current challenges,this review aims to identify potential areas for improvement.These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.
基金financial support from Natural Science Foundation of China (No.22161005)Guangxi Natural Science Foundation (Nos.2021GXNSFDA075005,2024GXNSFFA010001)。
文摘Albeit notable endeavors in the construction of organophosphorodithioates,the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge.Herein,an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine.This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields(up to 98 %yield) with high stereoselectivities(up to 97 % ee and >99:1 E/Z).
基金Financial supports from the National Natural Science Foundation of China(Nos.22271176,22371171)the Taishan Scholar Project of Shandong Province(No.tsqn202306015)Shandong University were gratefully appreciated.
文摘Sulfoxides and sulfide compounds have broad-spectrum biological properties and have received considerable attention in the past few decades.Herein we reported two metal and oxidant-free,practical and efficient methods for the synthesis of highly synthetically useful and structurally diverse ortho-aminoaryl sulfoxides and 3,4,5-trisubstituted oxazolones from readily accessible N-arylhydroxylamines and N-thiophthalimides.This rapid transformation occurred smoothly to achieve chemo-and regioselective cascade rearrangements due to the differences of the protecting-groups of the nitrogen atom of N-arylhydroxyamines.DFT studies suggested that the competing S-O and S-C bond formations via SN2 nucleophilic substitution are crucial for the observed protecting-group-dependent chemoselectivity.Subsequent applications have shown that these two protocols might be powerful tools for the construction of sulfur-containing complex molecules under simple conditions.
基金Science and Technology Foundation of Guizhou Province(No.QKHJC-ZK[2024]654)Guizhou Provincial University Key Laboratory of Advanced Functional Electronic Materials(No.QJ[2023]021).
文摘Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations.Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds.In comparison with traditional thermal or metal-mediated carbene transfer reactions,visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules.Recently,visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation,mild condition,high atom economy and rich structural diversity.This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles.The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review.The future research direction and challenges in this area are also discussed.
基金financially supported by the National Key R&D Program of China(2023YFC3905400)the Clean Combustion and Low-carbon Utilization of Coal,Strategic Priority Research Program of the Chinese Academy of Sciences,Grant No.XDA 29000000.
文摘The carbonylation of amines offers a promising route for synthesizing N-substituted carbamates with high atom economy.However,conventional catalysts exhibit limited catalytic efficiency,and the underlying proton transfer mechanism remains elusive.Herein,we reported a metal-free,room-temperature strategy utilizing 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)as a dual hydrogen bond catalyst to synergistically activate propylamine(PA)and dimethyl carbonate(DMC).This green catalytic system achieves a 10-fold acceleration in reaction rate compared to other hydrogen bonding catalysts under mild conditions.This is enabled by dual hydrogen bonding of TBD with PA and DMC,which facilitates rapid proton transfer and stabilizes tetrahedral intermediates.Theoretical calculations confirm that the dual hydrogen bond system significantly lowers activation energy compared to single hydrogen bond analogs.Furthermore,it was revealed that the hydrogen bonding network within the product is the primary factor responsible for the sluggish reaction rate.This study demonstrates the effectiveness of a dual hydrogen bond system in accelerating the carbonylation of amines and provides a green route to access carbamates.
