Over the past few decades,N-sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis,allowing for diverse innovative and original chemical transformations t...Over the past few decades,N-sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis,allowing for diverse innovative and original chemical transformations that were otherwise difficult to achieve.This critical review summarizes the major advancements in the carbene chemistry of N-sulfonyl hydrazones.The contents of this review are organized based on research conducted by leading scientists who have made significant contributions to this field.The individual carbene transfer reactions and their mechanisms,as well as the potential applications in the synthesis of natural products and complex bioactive molecules,are thoroughly discussed.展开更多
A simple,practical and eco-friendly visible light-induced alkylation of N-sulfonyl ketamine under metal-,additive-,external photocatalyst-free conditions was developed.This photocatalytic method utilized low cost and ...A simple,practical and eco-friendly visible light-induced alkylation of N-sulfonyl ketamine under metal-,additive-,external photocatalyst-free conditions was developed.This photocatalytic method utilized low cost and abundant alkanes as the atom economy alkyl sources with H2O2as the environmentally beneficial oxidant,allowing for the efficient construction of diverse valuable 4-alkylated sulfonyl ketamines.The N-sulfonyl ketamine played a dual role of reactant and photocatalyst,thus simplifying the reaction system.展开更多
A diastereoselectivity-controllable formal[3+2]-cycloaddition of arylvinyl oxirane 2,2-diesters with cyclic N-sulfonyl imines is developed,affording the corresponding tricyclic oxazolidine derivatives in moderate to e...A diastereoselectivity-controllable formal[3+2]-cycloaddition of arylvinyl oxirane 2,2-diesters with cyclic N-sulfonyl imines is developed,affording the corresponding tricyclic oxazolidine derivatives in moderate to excellent yields with excellent diastereoselectivities in the presence of palladium(0)or scandium(III)triflate.This protocol allows selective synthesis of diastereomers of tricyclic oxazolidine derivatives under switchable and mild conditions.Further transformations of the obtained products were conducted by removing ester groups and arylvinyl moieties.展开更多
Fluoroalkyl N-sulfonyl hydrazones are versatile reagents that can be used to synthesize a wide range of diverse fluoroalkylated organic molecules.Although it has been known since 1975,the chemistry of fluoroalkyl N-su...Fluoroalkyl N-sulfonyl hydrazones are versatile reagents that can be used to synthesize a wide range of diverse fluoroalkylated organic molecules.Although it has been known since 1975,the chemistry of fluoroalkyl N-sulfonyl hydrazones has recently only received great attention from the scientific community.Generally,they are used as either safe and bench-stable diazo precursors in carbene transfer reactions or as 1,3-dipoles in cycloaddition and cyclization reactions.Notably,fluoroalkyl N-sulfonyl hydrazones to replace toxic fluoroalkyl diazo compounds in carbene transfer reactions reduce the risk of rapid accumulation of explosive diazo compounds and improve functional group compatibility and substrate scope.Given the growing importance of fluoroalkyl N-sulfonyl hydrazones in chemical synthesis,a comprehensive review of this topic in the literature is essential to demonstrate their synthetic potential.In this review,we critically summarize and comprehensively analyze the publications in various literatures on the chemistry of fluoroalkyl N-sulfonyl hydrazones starting from 1990 to date.The classification of the different reactivity profiles of fluoroalkyl N-sulfonyl hydrazones and the efficiencies of similar types of reactions or substrates with fluoroalkyl diazo compounds are compared.展开更多
The easily prepared and recoverable chiral N-sulfonylated fl-amino alcohol 2 in combination with Ti（OPr-i）4 was found to be an effective chiral catalyst for the enantioselective addition of alkynylzinc to ketones, w...The easily prepared and recoverable chiral N-sulfonylated fl-amino alcohol 2 in combination with Ti（OPr-i）4 was found to be an effective chiral catalyst for the enantioselective addition of alkynylzinc to ketones, which gave the useful products, i.e. chiral tertiary propargyl alcohols, with the ee up to 92%.展开更多
Polymers with metal coordination ability are outstanding precursors of nanocatalysts,attracting numerous attention in nanocatalysis area.It has been rarely reported for the poly(N-sulfonyl amidines)as macromolecular l...Polymers with metal coordination ability are outstanding precursors of nanocatalysts,attracting numerous attention in nanocatalysis area.It has been rarely reported for the poly(N-sulfonyl amidines)as macromolecular ligands for nanocatalysis.Herein,a catalyst-free multicomponent polymerization(MCP)strategy is developed to facilely prepare a library of amphiphilic poly(Nsulfonyl amidines)with zwitterionic properties starting from disulfonyl azide,hydrophilic dialdehyde and cyclic amino acids including proline and pipecolinic acid.Metals or additives can be thorougly avoided through this method.All the obtained polymers have well-defined structures,high yields and weight-average molecular weights(M_(w)s,up to 99,300 g/mol).The unique zwitterionic property,amphiphilicity and Cu(Ⅰ)coordination ability of the obtained poly(N-sulfonyl amidines)endow them to form the polymer-Cu(Ⅰ)complexes as nanocatalysts.Such nanocatalysts exhibit high catalytic efficiency in aqueous Cucatalyzed azide-alkyne cycloaddition(CuAAC)reaction at a low Cu(Ⅰ)loading of 50 ppm.Nanocatalysts with a high ratio of polymers to Cu(Ⅰ)have also been demonstrated with Cu(Ⅰ)stabilization ability.This work provides a“green”MCP method toward zwitterionic and amphiphilic poly(N-sulfonyl amidines),and highlights their unique potentials for nanocatalysis.展开更多
Anionic ring-opening polymerization(AROP)of N-sulfonyl aziridines is an important synthetic route to linear polyethyleneimine(PEI)and its derivatives.In most cases,inert atmosphere and dry solvent were needed because ...Anionic ring-opening polymerization(AROP)of N-sulfonyl aziridines is an important synthetic route to linear polyethyleneimine(PEI)and its derivatives.In most cases,inert atmosphere and dry solvent were needed because of the oxygen-and water-sensitive initiators/catalysts used.Therefore,the AROP of N-sulfonyl aziridines that can be entirely operated in air atmosphere is still a challenging task.Herein,we report a series of sulfanions,including xanthates,dithiocarbamates,dithiobenzoates,thioacetates,and thiolates,as the initiators for the AROP of N-sulfonyl aziridines.Due to their good stability,openvessel polymerization was achieved with high livingness,affording a range of well-definedα-,ω-telechelic poly(N-sulfonyl aziridine)homopolymers and block copolymers with narrow dispersities and tunable molecular weights.Theα-end group of these polyaziridines was readily converted to thiol group,which enabled further post-polymerization functionalization with benzyl acrylate and poly(ethylene glycol)via thiol-ene click chemistry.The establishment of open-vessel sulfanion-initiated AROP of N-sulfonyl aziridines thus lays a solid foundation for the bulk preparation and application of poly(N-sulfonyl aziridine)s and PEI derivatives.展开更多
基金the financial support from the National Natural Science Foundation of China(22331004)。
文摘Over the past few decades,N-sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis,allowing for diverse innovative and original chemical transformations that were otherwise difficult to achieve.This critical review summarizes the major advancements in the carbene chemistry of N-sulfonyl hydrazones.The contents of this review are organized based on research conducted by leading scientists who have made significant contributions to this field.The individual carbene transfer reactions and their mechanisms,as well as the potential applications in the synthesis of natural products and complex bioactive molecules,are thoroughly discussed.
基金financial support from the University of South China。
文摘A simple,practical and eco-friendly visible light-induced alkylation of N-sulfonyl ketamine under metal-,additive-,external photocatalyst-free conditions was developed.This photocatalytic method utilized low cost and abundant alkanes as the atom economy alkyl sources with H2O2as the environmentally beneficial oxidant,allowing for the efficient construction of diverse valuable 4-alkylated sulfonyl ketamines.The N-sulfonyl ketamine played a dual role of reactant and photocatalyst,thus simplifying the reaction system.
基金supported by the National Natural Science Foundation of China(21861008,21761006)Guangxi Natural Science Foundation(2018GXNSFBA138037)+1 种基金Department of Science and Technology of Guangxi(AD19245049)“BAGUI Scholar”Program of Guangxi Province of China。
文摘A diastereoselectivity-controllable formal[3+2]-cycloaddition of arylvinyl oxirane 2,2-diesters with cyclic N-sulfonyl imines is developed,affording the corresponding tricyclic oxazolidine derivatives in moderate to excellent yields with excellent diastereoselectivities in the presence of palladium(0)or scandium(III)triflate.This protocol allows selective synthesis of diastereomers of tricyclic oxazolidine derivatives under switchable and mild conditions.Further transformations of the obtained products were conducted by removing ester groups and arylvinyl moieties.
基金the National Natural Science Foundation of China(21871043,21961130376)Department of Science and Technology of Jilin Province(20180101185JC,20190701012GH,20200801065GH)the Fundamental Research Funds for the Central Universities(2412019ZD001,2412019FZ006)。
文摘Fluoroalkyl N-sulfonyl hydrazones are versatile reagents that can be used to synthesize a wide range of diverse fluoroalkylated organic molecules.Although it has been known since 1975,the chemistry of fluoroalkyl N-sulfonyl hydrazones has recently only received great attention from the scientific community.Generally,they are used as either safe and bench-stable diazo precursors in carbene transfer reactions or as 1,3-dipoles in cycloaddition and cyclization reactions.Notably,fluoroalkyl N-sulfonyl hydrazones to replace toxic fluoroalkyl diazo compounds in carbene transfer reactions reduce the risk of rapid accumulation of explosive diazo compounds and improve functional group compatibility and substrate scope.Given the growing importance of fluoroalkyl N-sulfonyl hydrazones in chemical synthesis,a comprehensive review of this topic in the literature is essential to demonstrate their synthetic potential.In this review,we critically summarize and comprehensively analyze the publications in various literatures on the chemistry of fluoroalkyl N-sulfonyl hydrazones starting from 1990 to date.The classification of the different reactivity profiles of fluoroalkyl N-sulfonyl hydrazones and the efficiencies of similar types of reactions or substrates with fluoroalkyl diazo compounds are compared.
基金Project supported by the National Natural Science Foundation of China （Nos. 29925205, 30271488, 20021001 and 203900501）.
文摘The easily prepared and recoverable chiral N-sulfonylated fl-amino alcohol 2 in combination with Ti（OPr-i）4 was found to be an effective chiral catalyst for the enantioselective addition of alkynylzinc to ketones, which gave the useful products, i.e. chiral tertiary propargyl alcohols, with the ee up to 92%.
基金supported by the National Natural Science Foundation of China(21978039)the Natural Science Foundation of Jiangsu Province(BK20221265,BK20211100)the Fundamental Research Funds for the Central Universities(DUT21YG133,DUT22YG224)。
文摘Polymers with metal coordination ability are outstanding precursors of nanocatalysts,attracting numerous attention in nanocatalysis area.It has been rarely reported for the poly(N-sulfonyl amidines)as macromolecular ligands for nanocatalysis.Herein,a catalyst-free multicomponent polymerization(MCP)strategy is developed to facilely prepare a library of amphiphilic poly(Nsulfonyl amidines)with zwitterionic properties starting from disulfonyl azide,hydrophilic dialdehyde and cyclic amino acids including proline and pipecolinic acid.Metals or additives can be thorougly avoided through this method.All the obtained polymers have well-defined structures,high yields and weight-average molecular weights(M_(w)s,up to 99,300 g/mol).The unique zwitterionic property,amphiphilicity and Cu(Ⅰ)coordination ability of the obtained poly(N-sulfonyl amidines)endow them to form the polymer-Cu(Ⅰ)complexes as nanocatalysts.Such nanocatalysts exhibit high catalytic efficiency in aqueous Cucatalyzed azide-alkyne cycloaddition(CuAAC)reaction at a low Cu(Ⅰ)loading of 50 ppm.Nanocatalysts with a high ratio of polymers to Cu(Ⅰ)have also been demonstrated with Cu(Ⅰ)stabilization ability.This work provides a“green”MCP method toward zwitterionic and amphiphilic poly(N-sulfonyl amidines),and highlights their unique potentials for nanocatalysis.
基金the National Natural Science Foundation of China(21905171,21774077)Shanghai Municipal Government(18JC1410800)。
文摘Anionic ring-opening polymerization(AROP)of N-sulfonyl aziridines is an important synthetic route to linear polyethyleneimine(PEI)and its derivatives.In most cases,inert atmosphere and dry solvent were needed because of the oxygen-and water-sensitive initiators/catalysts used.Therefore,the AROP of N-sulfonyl aziridines that can be entirely operated in air atmosphere is still a challenging task.Herein,we report a series of sulfanions,including xanthates,dithiocarbamates,dithiobenzoates,thioacetates,and thiolates,as the initiators for the AROP of N-sulfonyl aziridines.Due to their good stability,openvessel polymerization was achieved with high livingness,affording a range of well-definedα-,ω-telechelic poly(N-sulfonyl aziridine)homopolymers and block copolymers with narrow dispersities and tunable molecular weights.Theα-end group of these polyaziridines was readily converted to thiol group,which enabled further post-polymerization functionalization with benzyl acrylate and poly(ethylene glycol)via thiol-ene click chemistry.The establishment of open-vessel sulfanion-initiated AROP of N-sulfonyl aziridines thus lays a solid foundation for the bulk preparation and application of poly(N-sulfonyl aziridine)s and PEI derivatives.
