Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to ...Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to the inevitable side reactions involving cycloaddition.Herein,the visible-light-mediated O-H functionalization reactions of alkenyl alcohols with diazo compounds were developed.This process competed favorably with the cycloaddition reaction.A series of multifunctional ethers were provided in low to high yields with aryldiazoacetates or 3-diazooxindoles.Biologically relevant spirooxindole-fused oxacycle could be easily accessed from the O-H functionalization product of alkenyl alcohol and 3-diazooxindole.展开更多
The Rh(III)-catalyzed C—H functionalization of sulfoxonium ylides and successively annulation with two classes of cyclic diazo compounds has been realized,affording structurally diverse fused-ring or spirocyclic comp...The Rh(III)-catalyzed C—H functionalization of sulfoxonium ylides and successively annulation with two classes of cyclic diazo compounds has been realized,affording structurally diverse fused-ring or spirocyclic compounds under redoxneutral conditions.The reaction proceeds via successive chelation-assisted C—H activation,carbene insertion,and intramolecular[3+3]/[4+1]annulation processes.展开更多
Transition metal-catalyzed carbene transfer reaction is one of the most notable advances for C-C bond formation reactionsduring the past decade,which has been widely employed in the preparation of C3-substituted indol...Transition metal-catalyzed carbene transfer reaction is one of the most notable advances for C-C bond formation reactionsduring the past decade,which has been widely employed in the preparation of C3-substituted indoles,Here,we described an efficient exa mple of catalyst-and metal-free aminobo ration of alkynes and C—C bond formation with diazo compounds to produce C3-substituted indoles,Diverse alkynyla nilines and diazo compounds ca n be utilized for this tandem transfo rmation under mild reaction conditions,re sulting in broad functional group co mpatibility.Additionally,this metal-free strategy can be extended to construct substituted benzofurans.展开更多
A[Cp*RhCl_(2)]_(2)-catalyzed intramolecular annulation reaction via aminoalkylation of alkenes with diazo compounds has been developed to construct highly-functionalized isoindolinones.This approach exhibits step econ...A[Cp*RhCl_(2)]_(2)-catalyzed intramolecular annulation reaction via aminoalkylation of alkenes with diazo compounds has been developed to construct highly-functionalized isoindolinones.This approach exhibits step economy,mild reaction conditions,and good functional group tolerance,facilitating access to a wide range of highly-valuable functionalized isoindolinones with high level of yields(up to 99%yield).展开更多
Direct enantioselective allylic C—H functionalization has emerged as a powerful strategy for the asymmetric syn-thesis of highly valuable chiral products.Herein,a Rh(III)-catalyzed enantioselective allylic C—H alkyl...Direct enantioselective allylic C—H functionalization has emerged as a powerful strategy for the asymmetric syn-thesis of highly valuable chiral products.Herein,a Rh(III)-catalyzed enantioselective allylic C—H alkylation of unactivated alkenes withα-diazo carbonyl compounds is described,enabling direct access to chiral products with high efficiency(up to 77%yield,92%ee,and>10∶1 B/L(branched/linear)selectivity).This atom-and step-economical protocol directly converts simple,unactivated substrates into valuable enantioenriched products under mild conditions,providing an efficient catalytic system for asymmetric allylic C—H functionalization.展开更多
Diazo compounds are generally used as carbene precursors. Traditionally, dirhodium, copper and iron catalysts were used to decompose diazo compounds to form the key metal carbene intermediates. Recently, the gold cata...Diazo compounds are generally used as carbene precursors. Traditionally, dirhodium, copper and iron catalysts were used to decompose diazo compounds to form the key metal carbene intermediates. Recently, the gold catalysts have been developed as a unique type of metal catalyst to decompose diazo compounds. The derived gold carbene showed much different characters comparing with other transition metal carbenes. They could go through a series of cycloaddition, insertion and coupling reactions. Here, the recent progress of the gold carbene chemistry from diazo compounds was reviewed, including the scope of reactions,mechanism and synthetic applications.展开更多
The palladium（o）-catalyzed nitrogen insertion into cyclic Si-Si bonds has been realized by using N-tosylhydrazones/diazo compounds as the nitrogen source. The palladium（Ⅱ） nitrene formation and subsequent migrato...The palladium（o）-catalyzed nitrogen insertion into cyclic Si-Si bonds has been realized by using N-tosylhydrazones/diazo compounds as the nitrogen source. The palladium（Ⅱ） nitrene formation and subsequent migratory insertion process are proposed as the key steps for this reaction.展开更多
A visible-light induced decarboxylative aza-Darzens reaction between N-aryl glycines and diazo compounds was developed, which affords various mono-substituted aziridines in good yields.
A simple and efficient process involving the Rh(II)-catalyzed[1+1+3]annulation of diazooxindoles and vinyl azides has been developed for the synthesis of spiropyrrolidine oxindoles with potential biological activity a...A simple and efficient process involving the Rh(II)-catalyzed[1+1+3]annulation of diazooxindoles and vinyl azides has been developed for the synthesis of spiropyrrolidine oxindoles with potential biological activity and significant synthetic applications.This process involves a novel rhodium-catalyzed olefination of diazo compounds,followed by annulation with vinyl azides.This method is compatible with a broad range of substrates and affords moderate to good yields under mild reaction conditions.展开更多
Catalytic asymmetric dearomatization(CADA)has emerged as a powerful strategy for transforming planar aromatic systems into three-dimensional chiral architectures[1].Notably,the Büchner reaction and arene cyclopro...Catalytic asymmetric dearomatization(CADA)has emerged as a powerful strategy for transforming planar aromatic systems into three-dimensional chiral architectures[1].Notably,the Büchner reaction and arene cyclopropanation excel in constructing complex polycyclic frameworks[2].However,current methods predominantly rely on diazo compounds as carbene precursors(Scheme1a),which pose safety risks and limit functional group compatibility.展开更多
A convenient photocatalytic multi-component reaction of alkenes,quinoxalin-2(1H)-ones,and diazo compounds has been developed in the presence of water.A number of ester-containing quinoxalin-2(1H)-ones could be efficie...A convenient photocatalytic multi-component reaction of alkenes,quinoxalin-2(1H)-ones,and diazo compounds has been developed in the presence of water.A number of ester-containing quinoxalin-2(1H)-ones could be efficiently obtained in moderate to good yields at room temperature.This metal-free visiblelight-driven tandem reaction was conducted through proton-coupled electron transfer(PCET)process using water as the hydrogen donor and 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene(4CzIPN)as the photocatalyst.展开更多
Bichner reaction,as a unique type of expansive dearomatization,has become a practical strategy for the straightforward assembly of valuable functionalized cycloheptatrienes from ubiquitous aromatic precursors.Although...Bichner reaction,as a unique type of expansive dearomatization,has become a practical strategy for the straightforward assembly of valuable functionalized cycloheptatrienes from ubiquitous aromatic precursors.Although the asymmetric version has been investigated since the early 1990s,enantioselective Bichner reaction is still limited by the catalyst type and substrate scope.This review aims to propose the limitation and possible development direction of this field by summarizing the evolution of catalytic asymmetric Bichner reaction,which is organized on the basis of intra-and intermolecular reactions.Considering the different metal carbene precursors,the reactions are further classified by carbene sources.展开更多
α,α-Difluoro-β-aminophosphonates can be looked as structural analogies withα-amino acids,which have attracted great attention in biological and medicinal chemistry during the past decades.Furthermore,these compoun...α,α-Difluoro-β-aminophosphonates can be looked as structural analogies withα-amino acids,which have attracted great attention in biological and medicinal chemistry during the past decades.Furthermore,these compounds also belong to an important type of organic building blocks for the rapid synthesis of difluoromethylenephosphonate-containing molecules.Thus,the preparation and application ofα,α-difluoro-β-aminophosphonates are hot research topics in organic phosphine chemistry.A comprehensive summary of the literature reports related toα,α-difluoro-β-aminophosphonates in recent years is presented.And aspects of synthesis and applications ofα,α-difluoro-β-aminophosphonates are discussed,in order to provide critical guidance for the further development of reactions and applications for the synthesis of difluoromethylenephosphonate derivatives.展开更多
Phosphine-relayed olefination and aza-Wittig reactions of readily available aldehydes with 2,2,2-trifluorodiazoethane （CF3CHN2） have been realized. This protocol enables the facile construction of a series of triflu...Phosphine-relayed olefination and aza-Wittig reactions of readily available aldehydes with 2,2,2-trifluorodiazoethane （CF3CHN2） have been realized. This protocol enables the facile construction of a series of trifluoromethylated alkenes and hydrazones in good to high yield under mild conditions.展开更多
A silver-catalyzed three-component coupling reaction of carbon dioxide, amines and α-diazoesters has been developed for the first time. The novel reaction provides an efficient and practical methodology for the synth...A silver-catalyzed three-component coupling reaction of carbon dioxide, amines and α-diazoesters has been developed for the first time. The novel reaction provides an efficient and practical methodology for the synthesis of a wide range of new α-carbamoyloxy esters, which are difficult to prepare by existing methods. The advantages of the method include the use of readily available starting materials, simple catalytic system, good atom economy and high functional group tolerance.展开更多
A novel generation of oxazole vlide and interception with sulfonamide have been well developed to construct fully substituted amidines. This copper-catalyzed four-component reaction incorporates two diazo molecules to...A novel generation of oxazole vlide and interception with sulfonamide have been well developed to construct fully substituted amidines. This copper-catalyzed four-component reaction incorporates two diazo molecules to target amidines and shows broad substrate scope, excellent functional groups tolerance and good to excellent yields.展开更多
A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported.The reaction occurred under sole visible light irradiation...A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported.The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives,affording the corresponding sulfoxonium ylides in moderate to good yields.The success of late-stage modification of natural isolates or drug candidates,scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.展开更多
A copper-mediated deuterotrifluoromethylation of α-diazo esters under the promotion of deuterium oxide （D20） has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluor...A copper-mediated deuterotrifluoromethylation of α-diazo esters under the promotion of deuterium oxide （D20） has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluoromethyl- ation reaction is of broad scope and can afford the deuterated products with higher than 99% isotopic purity. More- over, the results of this investigation also provide some experimental evidences to support our previously proposed trifluoromethylation mechanism.展开更多
文摘Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to the inevitable side reactions involving cycloaddition.Herein,the visible-light-mediated O-H functionalization reactions of alkenyl alcohols with diazo compounds were developed.This process competed favorably with the cycloaddition reaction.A series of multifunctional ethers were provided in low to high yields with aryldiazoacetates or 3-diazooxindoles.Biologically relevant spirooxindole-fused oxacycle could be easily accessed from the O-H functionalization product of alkenyl alcohol and 3-diazooxindole.
文摘The Rh(III)-catalyzed C—H functionalization of sulfoxonium ylides and successively annulation with two classes of cyclic diazo compounds has been realized,affording structurally diverse fused-ring or spirocyclic compounds under redoxneutral conditions.The reaction proceeds via successive chelation-assisted C—H activation,carbene insertion,and intramolecular[3+3]/[4+1]annulation processes.
基金supported by the National Natural Science Foundation of China (Nos.21972064 and 21672097)the Excellent Youth Foundation of Jiangsu Scientific Committee (No. BK20180007)the“Innovation & Entrepreneurship Talents Plan” of Jiangsu Province。
文摘Transition metal-catalyzed carbene transfer reaction is one of the most notable advances for C-C bond formation reactionsduring the past decade,which has been widely employed in the preparation of C3-substituted indoles,Here,we described an efficient exa mple of catalyst-and metal-free aminobo ration of alkynes and C—C bond formation with diazo compounds to produce C3-substituted indoles,Diverse alkynyla nilines and diazo compounds ca n be utilized for this tandem transfo rmation under mild reaction conditions,re sulting in broad functional group co mpatibility.Additionally,this metal-free strategy can be extended to construct substituted benzofurans.
文摘A[Cp*RhCl_(2)]_(2)-catalyzed intramolecular annulation reaction via aminoalkylation of alkenes with diazo compounds has been developed to construct highly-functionalized isoindolinones.This approach exhibits step economy,mild reaction conditions,and good functional group tolerance,facilitating access to a wide range of highly-valuable functionalized isoindolinones with high level of yields(up to 99%yield).
文摘Direct enantioselective allylic C—H functionalization has emerged as a powerful strategy for the asymmetric syn-thesis of highly valuable chiral products.Herein,a Rh(III)-catalyzed enantioselective allylic C—H alkylation of unactivated alkenes withα-diazo carbonyl compounds is described,enabling direct access to chiral products with high efficiency(up to 77%yield,92%ee,and>10∶1 B/L(branched/linear)selectivity).This atom-and step-economical protocol directly converts simple,unactivated substrates into valuable enantioenriched products under mild conditions,providing an efficient catalytic system for asymmetric allylic C—H functionalization.
基金supported by the National Natural Science Foundation of China(21372144)China Postdoctoral Science Foundation,the Fundamental Research Funds of Shandong University(2014JC008)the Subject Construction Funds of Shandong University(104.205.2.5)
文摘Diazo compounds are generally used as carbene precursors. Traditionally, dirhodium, copper and iron catalysts were used to decompose diazo compounds to form the key metal carbene intermediates. Recently, the gold catalysts have been developed as a unique type of metal catalyst to decompose diazo compounds. The derived gold carbene showed much different characters comparing with other transition metal carbenes. They could go through a series of cycloaddition, insertion and coupling reactions. Here, the recent progress of the gold carbene chemistry from diazo compounds was reviewed, including the scope of reactions,mechanism and synthetic applications.
基金The project is supported by the National Basic Research Pro- gram of China （973 Program, No. 2015CB856600） and the Natio- anal Natural Science Foundation of China （Grant 21332002, 21472004）.
文摘The palladium（o）-catalyzed nitrogen insertion into cyclic Si-Si bonds has been realized by using N-tosylhydrazones/diazo compounds as the nitrogen source. The palladium（Ⅱ） nitrene formation and subsequent migratory insertion process are proposed as the key steps for this reaction.
基金supported by the National Natural Science Foundation of China(2147224921202207)+1 种基金the Pearl River S&T Nova Program of Guangzhou(2013J2200017)the Fundamental Research Funds for the Central Universities(14lgzd05)
文摘A visible-light induced decarboxylative aza-Darzens reaction between N-aryl glycines and diazo compounds was developed, which affords various mono-substituted aziridines in good yields.
基金supported by the National Natural Science Foundation of China(21572225)~~
文摘A simple and efficient process involving the Rh(II)-catalyzed[1+1+3]annulation of diazooxindoles and vinyl azides has been developed for the synthesis of spiropyrrolidine oxindoles with potential biological activity and significant synthetic applications.This process involves a novel rhodium-catalyzed olefination of diazo compounds,followed by annulation with vinyl azides.This method is compatible with a broad range of substrates and affords moderate to good yields under mild reaction conditions.
文摘Catalytic asymmetric dearomatization(CADA)has emerged as a powerful strategy for transforming planar aromatic systems into three-dimensional chiral architectures[1].Notably,the Büchner reaction and arene cyclopropanation excel in constructing complex polycyclic frameworks[2].However,current methods predominantly rely on diazo compounds as carbene precursors(Scheme1a),which pose safety risks and limit functional group compatibility.
基金supported by Sichuan Science and Technology Program(No.2023NSFSC0101)the 2024 Provincial platform project of Chengdu Normal University(No.GNFZ202404)+1 种基金Natural Science Foundation of Shandong Province(No.ZR2021MB065)National Natural Science Foundation of China(No.22101237)。
文摘A convenient photocatalytic multi-component reaction of alkenes,quinoxalin-2(1H)-ones,and diazo compounds has been developed in the presence of water.A number of ester-containing quinoxalin-2(1H)-ones could be efficiently obtained in moderate to good yields at room temperature.This metal-free visiblelight-driven tandem reaction was conducted through proton-coupled electron transfer(PCET)process using water as the hydrogen donor and 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene(4CzIPN)as the photocatalyst.
基金support from MoST(No.2021YFC2100100)the National Natural Science Foundation of China(No.22125108)Yunnan Normal University,and Applied Basic Research Projects of Yunnan Province(No.202101AT070217).
文摘Bichner reaction,as a unique type of expansive dearomatization,has become a practical strategy for the straightforward assembly of valuable functionalized cycloheptatrienes from ubiquitous aromatic precursors.Although the asymmetric version has been investigated since the early 1990s,enantioselective Bichner reaction is still limited by the catalyst type and substrate scope.This review aims to propose the limitation and possible development direction of this field by summarizing the evolution of catalytic asymmetric Bichner reaction,which is organized on the basis of intra-and intermolecular reactions.Considering the different metal carbene precursors,the reactions are further classified by carbene sources.
文摘α,α-Difluoro-β-aminophosphonates can be looked as structural analogies withα-amino acids,which have attracted great attention in biological and medicinal chemistry during the past decades.Furthermore,these compounds also belong to an important type of organic building blocks for the rapid synthesis of difluoromethylenephosphonate-containing molecules.Thus,the preparation and application ofα,α-difluoro-β-aminophosphonates are hot research topics in organic phosphine chemistry.A comprehensive summary of the literature reports related toα,α-difluoro-β-aminophosphonates in recent years is presented.And aspects of synthesis and applications ofα,α-difluoro-β-aminophosphonates are discussed,in order to provide critical guidance for the further development of reactions and applications for the synthesis of difluoromethylenephosphonate derivatives.
基金This work was supported financially by the National Natural Science Foundation of China （Nos. 21225208, 21472137, and 21532008）, the National Basic Research Program of China （973 Program： Nos. 2014CB745100, 2015CB856500）, and the Tianjin Municipal Science ＆ Technology Commission （No. 14JCQNJC06200）.
文摘Phosphine-relayed olefination and aza-Wittig reactions of readily available aldehydes with 2,2,2-trifluorodiazoethane （CF3CHN2） have been realized. This protocol enables the facile construction of a series of trifluoromethylated alkenes and hydrazones in good to high yield under mild conditions.
文摘A silver-catalyzed three-component coupling reaction of carbon dioxide, amines and α-diazoesters has been developed for the first time. The novel reaction provides an efficient and practical methodology for the synthesis of a wide range of new α-carbamoyloxy esters, which are difficult to prepare by existing methods. The advantages of the method include the use of readily available starting materials, simple catalytic system, good atom economy and high functional group tolerance.
文摘A novel generation of oxazole vlide and interception with sulfonamide have been well developed to construct fully substituted amidines. This copper-catalyzed four-component reaction incorporates two diazo molecules to target amidines and shows broad substrate scope, excellent functional groups tolerance and good to excellent yields.
基金the National Natural Science Foundation of China(Nos.21971001 and 21702001)the Natural Science Foundation of Anhui Province(No.1808085MB47)the Open Fund for Discipline Construction,Institute of Physical Science and Information Technology,Anhui University,and the Start-Up Grant from Anhui University for financial support of this work.
文摘A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported.The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives,affording the corresponding sulfoxonium ylides in moderate to good yields.The success of late-stage modification of natural isolates or drug candidates,scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.
文摘A copper-mediated deuterotrifluoromethylation of α-diazo esters under the promotion of deuterium oxide （D20） has been developed for the synthesis of deuterium-labeled trifluoromethyl compounds. This deuterotrifluoromethyl- ation reaction is of broad scope and can afford the deuterated products with higher than 99% isotopic purity. More- over, the results of this investigation also provide some experimental evidences to support our previously proposed trifluoromethylation mechanism.
