Lignin is the only largest renewable aromatic resource in nature.Currently,most lignin is underutilized for low-value applications due to the complex structure and recalcitrant chemical properties.Over the past decade...Lignin is the only largest renewable aromatic resource in nature.Currently,most lignin is underutilized for low-value applications due to the complex structure and recalcitrant chemical properties.Over the past decades,extensive research has been devoted to valorizing lignin into aromatic N-heterocycles in the presence of nitrogen sources.It overcomes the element limitation,expands the products portfolio and would play a momentous role in value-added biorefinery concept.In this review,the latest research progress in the synthesis of N-heterocyclic compounds from lignin,lignin model compounds,and lignin-derived monomers(phenols,aromatic alcohols,aldehydes,ketones,and ethers)is presented.According to the structural characteristics of the products,these achievements are classified by the construction of five-,six-,and seven-membered N-heterocyclic compounds through one-step,multi-step,or one-pot multi-step reactions.Furthermore,the tailor-designed routes and catalytic systems,along with the reaction mechanisms/pathways involved are entirely discussed to elucidate the challenges regarding the structural complexity of lignin,the incompatible catalysis for C–O cleavage and C–N formation,as well as the nitrogen-heterocyclic ring construction.The prospects,future research efforts and process developments for the refining of lignin into aromatic N-heterocyclic compounds are outlined in terms of economy,environmental friendliness,and safety so as to draw some guidelines for lignin valorization.展开更多
Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strateg...Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strategy for the functionalization and conversion of C-H bonds of 1,4-naphthoquinones into C-N bonds,providing an effective route to synthesize 2-(N-substituted amino)-1,4-naphthoquinone with high yield under mild conditions.Additionally,the synergistic catalytic mechanism was investigated by 1H NMR titration experiments and LC-MS analysis,with experimental results sufficiently and consistently supporting the proposed mechanism of the catalytic cycle.展开更多
Compared to the widely used carbon-centered radicals,N-radicals have been relatively unexplored owing to the lack of practical and convenient production methods.Over the past few years,benefitting from the resurgence ...Compared to the widely used carbon-centered radicals,N-radicals have been relatively unexplored owing to the lack of practical and convenient production methods.Over the past few years,benefitting from the resurgence of reliable and controllable radical chemistry,N-radicals have been produced via thermal decomposition,oxidants,metal salts,or electrocatalysis.Therefore,numerous N-radical enabled cyclization of 1,n-enynes methods have been developed,providing a versatile and concise synthetic platform for the preparation of complex cyclic systems and natural products containing elaborate ring frameworks.In this review,we will summarize recent advances in the promising field of radical chemistry focusing on the production methods of N-radicals and their cyclization patterns,associated mechanisms,unmet challenges,and future opportunities.展开更多
Urea and oxalic acid are critical component in various chemical manufacturing industries.However,achieving simultaneous generation of urea and oxalic acid in a continuous-flow electrolyzer is a challenge.Herein,we rep...Urea and oxalic acid are critical component in various chemical manufacturing industries.However,achieving simultaneous generation of urea and oxalic acid in a continuous-flow electrolyzer is a challenge.Herein,we report a continuous-flow electrolyzer equipped with 9-square centime-ter-effective area gas diffusion electrodes(GDE)which can simultaneously catalyze the glycerol oxidation reaction in the anode region and the reduction reaction of CO_(2) and nitrate in the cathode region,producing oxalic acid and urea at both the anode and cathode,respectively.The current density at low cell voltage(0.9 V)remained above 18.7 mA cm^(-2) for 10 consecutive electrolysis cycles(120 h in total),and the Faraday efficiency of oxalic acid(67.1%) and urea(70.9%)did not decay.Experimental and theoretical studies show that in terms of the formation of C-N bond at the cathode,Pd-sites can provide protons for the hydrogenation process of CO_(2) and NO_(3)^(-),Cu-sites can promote the generation of *COOH and Bi-sites can stabilize *COOH.In addition,in terms of glycerol oxidation,the introduction of Cu and Bi into Pd metallene promotes the oxidation of hydroxyl groups and the cleavage of C-C bond in glycerol molecules,respectively.展开更多
Polynitrogen heterocycles are readily available and have recently arisen as versatile synthons for the formation of various C-C and C-X bonds,and medicinally active nitrogen-containing heterocycles.Several cascade rea...Polynitrogen heterocycles are readily available and have recently arisen as versatile synthons for the formation of various C-C and C-X bonds,and medicinally active nitrogen-containing heterocycles.Several cascade reactions,including annulation,radical cascade,and borylation reactions,have been reported in which polynitrogen heterocycles are applied as arylation reagents.The success of these exceptional reactions illustrates the great synthetic potential of polynitrogen heterocycles,which provides a direct and useful approach to arylation reactions and the synthesis of nitrogen-containing heterocycles.The use of photocatalysts to effectively transfer energy from visible light to non-absorbing compounds has gained increasing attention as this method allows for the mild and efficient generation of radicals in a controlled manner.This approach has thus led to new methods that involve unique bond formation reactions.In addition,the use of free radical intermediates stabilized by transition metal catalysts is a powerful way to construct new chemical bonds.The aim of this review is to highlight the rapidly expanding area of radical-initiated denitrogenative cascade reactions of polynitrogen heterocycles and elaborate on their mechanisms from a new perspective by using photocatalysis and metal-based catalysis.展开更多
Organic phosphorus compounds containing sp^(3)-C—P(O)bonds are increasingly widely applied in catalysis,pharmaceuticals,materials,pesticides,and other fields,and their synthesis has become a research hotspot in chemi...Organic phosphorus compounds containing sp^(3)-C—P(O)bonds are increasingly widely applied in catalysis,pharmaceuticals,materials,pesticides,and other fields,and their synthesis has become a research hotspot in chemistry.Diarylmethyl phosphine oxides are important organic phosphorus compounds containing sp^(3)-C—P(O)bonds,but their synthesis is limited.Traditional methods for their synthesis require the use of halogenated compounds and harsh reaction conditions.A new method for the copper-mediated synthesis of(diarylmethyl)diarylphosphine oxides has been developed.This method involves the cleavage of the sp^(3)-C—N bond in N-diarylmethylsulfonamides,leading to the formation of diarylmethyl carbocations.The carbocations then react with diarylphosphine oxides to construct sp^(3)-C—P(O)bonds.Our method only requires the addition of stoichiometric,inexpensive CuBr2 and produces a series of target compounds in satisfactory yields.Thus,it provides a convenient,and cost-effective pathway for the synthesis of diarylmethyl phosphine oxides.展开更多
A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as ...A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as starting materials,this method efficiently constructs a series ofα-,β-,γ-andδ-carbolines under alkaline conditions.The reaction proceeds smoothly in the presence of lithium tert-butoxide(t-BuOLi)or cesium carbonate(Cs_(2)CO_(3))without requiring transition metal catalysts,demonstrating good functional group tolerance.This approach enables gram-scale synthesis and has been successfully applied to the preparation of the organic material 2,6-CbPy,achieving high conversion efficiency.展开更多
Using 2,3-dichloro-5,6-dicyano-p-benzoquinone(DDQ)as the oxidant,we communicate an efficient oxidative C–N coupling of benzylic C–H bonds with amides to afford a series of amination products in good yields.A wide ra...Using 2,3-dichloro-5,6-dicyano-p-benzoquinone(DDQ)as the oxidant,we communicate an efficient oxidative C–N coupling of benzylic C–H bonds with amides to afford a series of amination products in good yields.A wide range of functional groups as well as various sulfonamides and carboxamides are well tolerated.Moreover,this reaction involves both the challenging C–H functionalization and C–N bond formation.展开更多
文摘Lignin is the only largest renewable aromatic resource in nature.Currently,most lignin is underutilized for low-value applications due to the complex structure and recalcitrant chemical properties.Over the past decades,extensive research has been devoted to valorizing lignin into aromatic N-heterocycles in the presence of nitrogen sources.It overcomes the element limitation,expands the products portfolio and would play a momentous role in value-added biorefinery concept.In this review,the latest research progress in the synthesis of N-heterocyclic compounds from lignin,lignin model compounds,and lignin-derived monomers(phenols,aromatic alcohols,aldehydes,ketones,and ethers)is presented.According to the structural characteristics of the products,these achievements are classified by the construction of five-,six-,and seven-membered N-heterocyclic compounds through one-step,multi-step,or one-pot multi-step reactions.Furthermore,the tailor-designed routes and catalytic systems,along with the reaction mechanisms/pathways involved are entirely discussed to elucidate the challenges regarding the structural complexity of lignin,the incompatible catalysis for C–O cleavage and C–N formation,as well as the nitrogen-heterocyclic ring construction.The prospects,future research efforts and process developments for the refining of lignin into aromatic N-heterocyclic compounds are outlined in terms of economy,environmental friendliness,and safety so as to draw some guidelines for lignin valorization.
基金2024 Special Talent Introduction Projects of Key R&D Program of Ningxia Hui Autonomous Region(2024BEH04049)the 2024 Guyuan City Innovation-Driven Achievement Transformation Project(2024BGTYF01-47)2025 Ningxia Natural Science Foundation Program(2025AAC030624).
文摘Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strategy for the functionalization and conversion of C-H bonds of 1,4-naphthoquinones into C-N bonds,providing an effective route to synthesize 2-(N-substituted amino)-1,4-naphthoquinone with high yield under mild conditions.Additionally,the synergistic catalytic mechanism was investigated by 1H NMR titration experiments and LC-MS analysis,with experimental results sufficiently and consistently supporting the proposed mechanism of the catalytic cycle.
文摘Compared to the widely used carbon-centered radicals,N-radicals have been relatively unexplored owing to the lack of practical and convenient production methods.Over the past few years,benefitting from the resurgence of reliable and controllable radical chemistry,N-radicals have been produced via thermal decomposition,oxidants,metal salts,or electrocatalysis.Therefore,numerous N-radical enabled cyclization of 1,n-enynes methods have been developed,providing a versatile and concise synthetic platform for the preparation of complex cyclic systems and natural products containing elaborate ring frameworks.In this review,we will summarize recent advances in the promising field of radical chemistry focusing on the production methods of N-radicals and their cyclization patterns,associated mechanisms,unmet challenges,and future opportunities.
文摘Urea and oxalic acid are critical component in various chemical manufacturing industries.However,achieving simultaneous generation of urea and oxalic acid in a continuous-flow electrolyzer is a challenge.Herein,we report a continuous-flow electrolyzer equipped with 9-square centime-ter-effective area gas diffusion electrodes(GDE)which can simultaneously catalyze the glycerol oxidation reaction in the anode region and the reduction reaction of CO_(2) and nitrate in the cathode region,producing oxalic acid and urea at both the anode and cathode,respectively.The current density at low cell voltage(0.9 V)remained above 18.7 mA cm^(-2) for 10 consecutive electrolysis cycles(120 h in total),and the Faraday efficiency of oxalic acid(67.1%) and urea(70.9%)did not decay.Experimental and theoretical studies show that in terms of the formation of C-N bond at the cathode,Pd-sites can provide protons for the hydrogenation process of CO_(2) and NO_(3)^(-),Cu-sites can promote the generation of *COOH and Bi-sites can stabilize *COOH.In addition,in terms of glycerol oxidation,the introduction of Cu and Bi into Pd metallene promotes the oxidation of hydroxyl groups and the cleavage of C-C bond in glycerol molecules,respectively.
文摘Polynitrogen heterocycles are readily available and have recently arisen as versatile synthons for the formation of various C-C and C-X bonds,and medicinally active nitrogen-containing heterocycles.Several cascade reactions,including annulation,radical cascade,and borylation reactions,have been reported in which polynitrogen heterocycles are applied as arylation reagents.The success of these exceptional reactions illustrates the great synthetic potential of polynitrogen heterocycles,which provides a direct and useful approach to arylation reactions and the synthesis of nitrogen-containing heterocycles.The use of photocatalysts to effectively transfer energy from visible light to non-absorbing compounds has gained increasing attention as this method allows for the mild and efficient generation of radicals in a controlled manner.This approach has thus led to new methods that involve unique bond formation reactions.In addition,the use of free radical intermediates stabilized by transition metal catalysts is a powerful way to construct new chemical bonds.The aim of this review is to highlight the rapidly expanding area of radical-initiated denitrogenative cascade reactions of polynitrogen heterocycles and elaborate on their mechanisms from a new perspective by using photocatalysis and metal-based catalysis.
文摘Organic phosphorus compounds containing sp^(3)-C—P(O)bonds are increasingly widely applied in catalysis,pharmaceuticals,materials,pesticides,and other fields,and their synthesis has become a research hotspot in chemistry.Diarylmethyl phosphine oxides are important organic phosphorus compounds containing sp^(3)-C—P(O)bonds,but their synthesis is limited.Traditional methods for their synthesis require the use of halogenated compounds and harsh reaction conditions.A new method for the copper-mediated synthesis of(diarylmethyl)diarylphosphine oxides has been developed.This method involves the cleavage of the sp^(3)-C—N bond in N-diarylmethylsulfonamides,leading to the formation of diarylmethyl carbocations.The carbocations then react with diarylphosphine oxides to construct sp^(3)-C—P(O)bonds.Our method only requires the addition of stoichiometric,inexpensive CuBr2 and produces a series of target compounds in satisfactory yields.Thus,it provides a convenient,and cost-effective pathway for the synthesis of diarylmethyl phosphine oxides.
基金Project supported by the National Natural Science Foundation of China(No.22371303)the Zhongshan Municipal Bureau of Science and Technology(Nos.2021B2014,CXTD2022013)the Shanghai Rising-Star Program(21QA1411000)。
文摘A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as starting materials,this method efficiently constructs a series ofα-,β-,γ-andδ-carbolines under alkaline conditions.The reaction proceeds smoothly in the presence of lithium tert-butoxide(t-BuOLi)or cesium carbonate(Cs_(2)CO_(3))without requiring transition metal catalysts,demonstrating good functional group tolerance.This approach enables gram-scale synthesis and has been successfully applied to the preparation of the organic material 2,6-CbPy,achieving high conversion efficiency.
基金supported by the National Basic Research Program of China(2011CB808600,2012CB725302)the National Natural Science Foundation of China(21390400,21272180,21302148)+2 种基金the Research Fund for the Doctoral Program of Higher Education of China(20120141130002)the Program for Changjiang Scholars and Innovative Research Team in University(IRT1030)The Program of Introducing Talents of Discipline to Universities of China(111 Program)is also appreciated
文摘Using 2,3-dichloro-5,6-dicyano-p-benzoquinone(DDQ)as the oxidant,we communicate an efficient oxidative C–N coupling of benzylic C–H bonds with amides to afford a series of amination products in good yields.A wide range of functional groups as well as various sulfonamides and carboxamides are well tolerated.Moreover,this reaction involves both the challenging C–H functionalization and C–N bond formation.
