Spinal cord injury involves non-reversible damage to the central nervous system that is characterized by limited regenerative capacity and secondary inflammatory damage.The expression of the C-C motif chemokine ligand...Spinal cord injury involves non-reversible damage to the central nervous system that is characterized by limited regenerative capacity and secondary inflammatory damage.The expression of the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis exhibits significant differences before and after injury.Recent studies have revealed that the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis is closely associated with secondary inflammatory responses and the recruitment of immune cells following spinal cord injury,suggesting that this axis is a novel target and regulatory control point for treatment.This review comprehensively examines the therapeutic strategies targeting the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis,along with the regenerative and repair mechanisms linking the axis to spinal cord injury.Additionally,we summarize the upstream and downstream inflammatory signaling pathways associated with spinal cord injury and the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis.This review primarily elaborates on therapeutic strategies that target the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis and the latest progress of research on antagonistic drugs,along with the approaches used to exploit new therapeutic targets within the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis and the development of targeted drugs.Nevertheless,there are presently no clinical studies relating to spinal cord injury that are focusing on the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis.This review aims to provide new ideas and therapeutic strategies for the future treatment of spinal cord injury.展开更多
Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenati...Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenation and C–C coupling limit the C_(2)H_(4)generation.Herein,CuxP/g-C_(3)N_(4) heterojunction prepared by an in-situ phosphating technique,achieved collaborative photocatalytic CO_(2) and H2O,producing CO and C_(2)H_(4)as the main products.Notably,the selectivity of C_(2)H_(4)produced by CuxP/g-C_(3)N_(4) attained to 64.25%,which was 9.85 times that of CuxP(6.52%).Detailed time-resolution photoluminescence spectra,femtosecond transient absorption spectroscopy tests and density functional theory(DFT)calculation validate the ultra-fast interfacial electron transfer mechanism in CuxP/g-C_(3)N_(4) heterojunction.Successive*H on P sites caused by adsorbed H2O splitting with moderate hydrogenation ability enables the multi-step hydrogenation during CO_(2)RR process over CuxP/g-C_(3)N_(4).With the aid of mediated asymmetric Cu and P dual sites by g-C_(3)N_(4) nanosheet,the produced*CHO shows an energetically favorable for C–C coupling.The coupling formed*CHOCHO further accepts photoexcited efficient e–and*H to deeply produce C_(2)H_(4)according to the C^(2+)intermediates,which has been detected by in-situ diffuse reflectance infrared Fourier transform spectroscopy and interpreted by DFT calculation.The novel insight mechanism offers an essential understanding for the development of CuxP-based heterojunctions for photocatalytic CO_(2) to C^(2+)value-added fuels.展开更多
Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit...Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit lower toxicity and a more mature preparation process.Unlike hydrogen fuel cells,DEFCs provide superior storage and transport feasibility,as well as cost-effectiveness,significantly enhancing their commercial viability.However,the stable C-C bond in ethanol creates a high activation energy barrier,often resulting in incomplete electrooxidation.Current commercial platinum(Pt)-and palladium(Pd)-based catalysts demonstrate low C-C bond cleavage efficiency(<7.5%),severely limiting DEFC energy output and power density.Furthermore,high catalyst costs and insufficient activity impede large-scale commercialization.Recent advances in DEFC anode catalyst design have focused on optimizing material composition and elucidating catalytic mechanisms.This review systematically examines developments in ethanol electrooxidation catalysts over the past five years,highlighting strategies to improve C1 pathway selectivity and C-C bond activation.Key approaches,such as alloying,nanostructure engineering,and interfacial synergy effects,are discussed alongside their mechanistic implications.Finally,we outline current challenges and future prospects for DEFC commercialization.展开更多
SF_6因具有良好的绝缘效果而被广泛地应用于电力系统中。但同时,SF_6也是一种温室气体,随着环境问题日益恶化,人们迫切需要找到替代SF_6的绝缘气体。为此,通过实验研究了环境友好气体c-C_4F_8及c-C_4F_8/N_2混合气体替代SF_6的可行性。...SF_6因具有良好的绝缘效果而被广泛地应用于电力系统中。但同时,SF_6也是一种温室气体,随着环境问题日益恶化,人们迫切需要找到替代SF_6的绝缘气体。为此,通过实验研究了环境友好气体c-C_4F_8及c-C_4F_8/N_2混合气体替代SF_6的可行性。通过调节电极间隙(1~6 mm)和气压(150~350 k Pa),测量了气体在不同条件下的击穿电压及击穿电流波形,得到了气体的绝缘特性并与SF_6气体进行了对比分析。实验结果表明:纯净的c-C_4F_8气体的绝缘强度约为SF_6的1.3倍,体积比为1:1的c-C_4F_8/N_2混合气体的绝缘强度约为与SF_6的0.9倍。通过计算,c-C_4F_8/N_2混合气体的液化温度可以达到电力系统使用要求。考虑到c-C_4F_8气体对于环境的影响较小,使用c-C_4F_8/N_2混合气体作为替代SF_6的绝缘气体,有着良好的应用前景。展开更多
A thoroughly mechanistic understanding of the electrochemical CO reduction reaction(eCORR)at the interface is significant for guiding the design of high-performance electrocatalysts.However,unintentionally ignored fac...A thoroughly mechanistic understanding of the electrochemical CO reduction reaction(eCORR)at the interface is significant for guiding the design of high-performance electrocatalysts.However,unintentionally ignored factors or unreasonable settings during mechanism simulations will result in false positive results between theory and experiment.Herein,we computationally identified the dynamic site preference change of CO adsorption with potentials on Cu(100),which was a previously unnoticed factor but significant to potential-dependent mechanistic studies.Combined with the different lateral interactions among adsorbates,we proposed a new C–C coupling mechanism on Cu(100),better explaining the product distribution at different potentials in experimental eCORR.At low potentials(from–0.4 to–0.6 V_(RHE)),the CO forms dominant adsorption on the bridge site,which couples with another attractively aggregated CO to form a C–C bond.At medium potentials(from–0.6 to–0.8 VRHE),the hollow-bound CO becomes dominant but tends to isolate with another adsorbate due to the repulsion,thereby blocking the coupling process.At high potentials(above–0.8 VRHE),the CHO intermediate is produced from the electroreduction of hollow-CO and favors the attraction with another bridge-CO to trigger C–C coupling,making CHO the major common intermediate for C–C bond formation and methane production.We anticipate that our computationally identified dynamic change in site preference of adsorbates with potentials will bring new opportunities for a better understanding of the potential-dependent electrochemical processes.展开更多
The selective addition reaction of unsaturated C-C bonds has always been a classic and constant research topic.Different from well-developed hydroboration,hydrosilylation,and hydrostannylation reaction,hydrogermylatio...The selective addition reaction of unsaturated C-C bonds has always been a classic and constant research topic.Different from well-developed hydroboration,hydrosilylation,and hydrostannylation reaction,hydrogermylation reaction remains challenging which hasn't been much reported.Herein,we developed a new metal-porous ligand polymers Pd1@POL-PPh_(n)Cy_(m)(n+m=3)with monoatomic dispersion characteristics for highly selective and efficient hydrogermylation of unsaturated C-C bonds,including alkynes,alkenes,and allenes.X-ray photoelectron spectroscopy and theoretical calculations further proved the introduction of cyclohexyl could gently adjust the charge on monoatomic Pd center which effectively facilitate the recognition and transformation of various substrates.With the electrically fine-tuned single atom palladium catalysts,we realized theα-germanium addition for the first time,obtaining corresponding allyl germanium and alkyl germanium compounds.展开更多
Pyridyl-based ketones and 1,6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products,p...Pyridyl-based ketones and 1,6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products,pharmaceuticals,organic materials and fine chemicals.In this context,we herein demonstrate an unprecedented,robust and generally applicable synthetically strategy to deliver these two crucial ketone frameworks via visible-light-induced ring-opening coupling reactions of cycloalcohols with vinylazaarenes and enones,respectively.A plausible mechanism involves the selectiveβ-C-C bond cleavage of cycloalcohols enabled by proton-coupled electron transfer and ensuing Giese-type addition followed by single electron reduction and protonation.The synthetic methodology exhibits broad substrate scope,excellent functional group compatibility as well as operational simplicity and environmental friendliness.展开更多
The oxidation of lignin model compounds to esters via C-C bond cleavage has attracted considerable attention,as esters could be used as important polymer precursors and pharmaceutical intermediates.However,most studie...The oxidation of lignin model compounds to esters via C-C bond cleavage has attracted considerable attention,as esters could be used as important polymer precursors and pharmaceutical intermediates.However,most studies focus on designing homogeneous or noble metal catalysts and conducting the reactions under basic conditions.Here,we report an efficient process for the C-C bond cleavage of lignin model compounds and selectively producing esters over different shaped CeO_(2)(i.e.,nanospheres(S),nanorods(R),nanoparticles(P),and nanocubes(C))under base-free conditions.Specifically,the yield of methyl anisate from the aerobic oxidation of l-(4-methoxyphenyl)ethanol reaches 77.6%over CeO_(2)-S in one hour(91%in 9 h),exhibiting higher performance compared to other evaluated CeO_(2)catalysts(6.4%-40.2%).Extensivecharacterizations and experimental investigations reveal that the density of weak base sites and oxygen vacancies on the CeO_(2)surface is positively correlated with the yield of methyl esters.Furthermore,the reaction pathway is investigated,which confirms that 1-(4-methoxyphenyl)ethanol first undergoes two reactions(i.e.,etherification and dehydrogenation)to produce intermediates of1-methoxy-4-(1-methoxy-ethyl)-benzene and 1-(4-methoxyphenyl)ethanone,respectively,followed by a series of functional group transformations to generate the targeted methyl anisate ultimately.展开更多
The carbon-carbon bond is the one of the most fundamental and abundant bonds that exist in organic molecules,and the challenge of functionalization of carbon-carbon bond has always been a critical pursuit in organic s...The carbon-carbon bond is the one of the most fundamental and abundant bonds that exist in organic molecules,and the challenge of functionalization of carbon-carbon bond has always been a critical pursuit in organic synthesis.In recent years,there have been a growing number of studies on the C-C bond activation.Nevertheless,the metal-catalyzed cleavage of the C-C(O)bond in unstrained ketones has remained relatively underexplored due to the strong affinity of carbonyl groups for metals.In this study,we report a nickel-catalyzed strategy for the reductive alkynylation of ketoimines viaβ-carbon elimination.This method involves the conversion of aryl ketones into aryl ketoimines,thus expanding the toolbox of aryl electrophiles.The use of a N-heterocyclic carbene(NHC)ligand is crucial for this catalytic transformation.This discovery leads to a cross electrophile coupling reaction characterized by its operational simplicity,unique chemo-selectivity and excellent functional group tolerance.In addition,the approach has been effectively applied to the late-stage alkynylation of diverse pharmaceuticals.Ultimately,a series of comprehensive experiments and theoretical studies were conducted to provide insights into the reaction pathway,which supports the proposedβ-carbon elimination process.展开更多
Copper(Cu)-based catalysts show significant potential for producing high value-added C_(2+)products in electrocatalytic CO_(2)/CO reduction reactions(CO(2)RR).However,the structural reconfiguration during operation po...Copper(Cu)-based catalysts show significant potential for producing high value-added C_(2+)products in electrocatalytic CO_(2)/CO reduction reactions(CO(2)RR).However,the structural reconfiguration during operation poses substantial challenges in identifying the intrinsic catalytic active site,especially under similar mass transport conditions.Herein,three typical and commercial Cu-based catalysts(Cu,CuO,and Cu_(2)O)are chosen as representatives to elucidate the structure-activity relationship of CORR in the membrane electrode assembly electrolyzer.Notably,only the Cu catalyst demonstrates the most suppression of hydrogen evolution reaction,thus achieving the highest FE of 86.7% for C_(2+)products at a current density of 500 mA cm^(-2) and maintaining a stable electrolysis over 110 h at a current of 200 mA cm^(-2).The influence of chemical valence state of Cu,electrochemical surface area,and local pH were firstly investigated and ruled out for the significant FE differences.Finally,based on the structure analysis from high resolution transmission electron microscope,OH-adsorption,in situ infrared spectroscopy and density functional theory calculations,it is suggested that the asymmetric C-C coupling(via ^(*)CHO and ^(*)CO)is the most probable reaction pathway for forming C_(2+)products,with Cu(100)-dominant grain boundaries(GBs)being the most favorable active sites.These findings provide deeper insights into the synergistic relationship between crystal facets and GBs in electrocatalytic systems.展开更多
基金supported by the National Natural Science Foundation of China(Key Program),No.11932013the National Natural Science Foundation of China(General Program),No.82272255+2 种基金Armed Police Force High-Level Science and Technology Personnel ProjectThe Armed Police Force Focuses on Supporting Scientific and Technological Innovation TeamsKey Project of Tianjin Science and Technology Plan,No.20JCZDJC00570(all to XC)。
文摘Spinal cord injury involves non-reversible damage to the central nervous system that is characterized by limited regenerative capacity and secondary inflammatory damage.The expression of the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis exhibits significant differences before and after injury.Recent studies have revealed that the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis is closely associated with secondary inflammatory responses and the recruitment of immune cells following spinal cord injury,suggesting that this axis is a novel target and regulatory control point for treatment.This review comprehensively examines the therapeutic strategies targeting the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis,along with the regenerative and repair mechanisms linking the axis to spinal cord injury.Additionally,we summarize the upstream and downstream inflammatory signaling pathways associated with spinal cord injury and the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis.This review primarily elaborates on therapeutic strategies that target the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis and the latest progress of research on antagonistic drugs,along with the approaches used to exploit new therapeutic targets within the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis and the development of targeted drugs.Nevertheless,there are presently no clinical studies relating to spinal cord injury that are focusing on the C-C motif chemokine ligand 2/C-C motif chemokine receptor 2 axis.This review aims to provide new ideas and therapeutic strategies for the future treatment of spinal cord injury.
文摘Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenation and C–C coupling limit the C_(2)H_(4)generation.Herein,CuxP/g-C_(3)N_(4) heterojunction prepared by an in-situ phosphating technique,achieved collaborative photocatalytic CO_(2) and H2O,producing CO and C_(2)H_(4)as the main products.Notably,the selectivity of C_(2)H_(4)produced by CuxP/g-C_(3)N_(4) attained to 64.25%,which was 9.85 times that of CuxP(6.52%).Detailed time-resolution photoluminescence spectra,femtosecond transient absorption spectroscopy tests and density functional theory(DFT)calculation validate the ultra-fast interfacial electron transfer mechanism in CuxP/g-C_(3)N_(4) heterojunction.Successive*H on P sites caused by adsorbed H2O splitting with moderate hydrogenation ability enables the multi-step hydrogenation during CO_(2)RR process over CuxP/g-C_(3)N_(4).With the aid of mediated asymmetric Cu and P dual sites by g-C_(3)N_(4) nanosheet,the produced*CHO shows an energetically favorable for C–C coupling.The coupling formed*CHOCHO further accepts photoexcited efficient e–and*H to deeply produce C_(2)H_(4)according to the C^(2+)intermediates,which has been detected by in-situ diffuse reflectance infrared Fourier transform spectroscopy and interpreted by DFT calculation.The novel insight mechanism offers an essential understanding for the development of CuxP-based heterojunctions for photocatalytic CO_(2) to C^(2+)value-added fuels.
基金supported by the National Natural Science Foundation of China(22472023,22202037)the Jilin Province Science and Technology Development Program(20250102077JC)the Fundamental Research Funds for the Central Universities(2412024QD014,2412023QD019).
文摘Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit lower toxicity and a more mature preparation process.Unlike hydrogen fuel cells,DEFCs provide superior storage and transport feasibility,as well as cost-effectiveness,significantly enhancing their commercial viability.However,the stable C-C bond in ethanol creates a high activation energy barrier,often resulting in incomplete electrooxidation.Current commercial platinum(Pt)-and palladium(Pd)-based catalysts demonstrate low C-C bond cleavage efficiency(<7.5%),severely limiting DEFC energy output and power density.Furthermore,high catalyst costs and insufficient activity impede large-scale commercialization.Recent advances in DEFC anode catalyst design have focused on optimizing material composition and elucidating catalytic mechanisms.This review systematically examines developments in ethanol electrooxidation catalysts over the past five years,highlighting strategies to improve C1 pathway selectivity and C-C bond activation.Key approaches,such as alloying,nanostructure engineering,and interfacial synergy effects,are discussed alongside their mechanistic implications.Finally,we outline current challenges and future prospects for DEFC commercialization.
文摘SF_6因具有良好的绝缘效果而被广泛地应用于电力系统中。但同时,SF_6也是一种温室气体,随着环境问题日益恶化,人们迫切需要找到替代SF_6的绝缘气体。为此,通过实验研究了环境友好气体c-C_4F_8及c-C_4F_8/N_2混合气体替代SF_6的可行性。通过调节电极间隙(1~6 mm)和气压(150~350 k Pa),测量了气体在不同条件下的击穿电压及击穿电流波形,得到了气体的绝缘特性并与SF_6气体进行了对比分析。实验结果表明:纯净的c-C_4F_8气体的绝缘强度约为SF_6的1.3倍,体积比为1:1的c-C_4F_8/N_2混合气体的绝缘强度约为与SF_6的0.9倍。通过计算,c-C_4F_8/N_2混合气体的液化温度可以达到电力系统使用要求。考虑到c-C_4F_8气体对于环境的影响较小,使用c-C_4F_8/N_2混合气体作为替代SF_6的绝缘气体,有着良好的应用前景。
文摘A thoroughly mechanistic understanding of the electrochemical CO reduction reaction(eCORR)at the interface is significant for guiding the design of high-performance electrocatalysts.However,unintentionally ignored factors or unreasonable settings during mechanism simulations will result in false positive results between theory and experiment.Herein,we computationally identified the dynamic site preference change of CO adsorption with potentials on Cu(100),which was a previously unnoticed factor but significant to potential-dependent mechanistic studies.Combined with the different lateral interactions among adsorbates,we proposed a new C–C coupling mechanism on Cu(100),better explaining the product distribution at different potentials in experimental eCORR.At low potentials(from–0.4 to–0.6 V_(RHE)),the CO forms dominant adsorption on the bridge site,which couples with another attractively aggregated CO to form a C–C bond.At medium potentials(from–0.6 to–0.8 VRHE),the hollow-bound CO becomes dominant but tends to isolate with another adsorbate due to the repulsion,thereby blocking the coupling process.At high potentials(above–0.8 VRHE),the CHO intermediate is produced from the electroreduction of hollow-CO and favors the attraction with another bridge-CO to trigger C–C coupling,making CHO the major common intermediate for C–C bond formation and methane production.We anticipate that our computationally identified dynamic change in site preference of adsorbates with potentials will bring new opportunities for a better understanding of the potential-dependent electrochemical processes.
基金supported by the National Natural Science Foundation of China(Nos.22201049,22471046)the Ba-Gui Youth Top-notch Talents Project of Guangxithe National HighLevel Personnel of Special Support Program for Young Top-notch Talents(9th batch)。
文摘The selective addition reaction of unsaturated C-C bonds has always been a classic and constant research topic.Different from well-developed hydroboration,hydrosilylation,and hydrostannylation reaction,hydrogermylation reaction remains challenging which hasn't been much reported.Herein,we developed a new metal-porous ligand polymers Pd1@POL-PPh_(n)Cy_(m)(n+m=3)with monoatomic dispersion characteristics for highly selective and efficient hydrogermylation of unsaturated C-C bonds,including alkynes,alkenes,and allenes.X-ray photoelectron spectroscopy and theoretical calculations further proved the introduction of cyclohexyl could gently adjust the charge on monoatomic Pd center which effectively facilitate the recognition and transformation of various substrates.With the electrically fine-tuned single atom palladium catalysts,we realized theα-germanium addition for the first time,obtaining corresponding allyl germanium and alkyl germanium compounds.
基金financial support from National Natural Science Foundation of China(Nos.21801129,22078153 and22378201)National Key Research and Development Program of China(No.2022YFB3805603)+3 种基金Natural science research projects in Jiangsu Higher Education Institutions(No.18KJB150018)Open Research Fund of School of Chemistry and Chemical EngineeringHenan Normal University(No.2024Y16)Nanjing Tech University(Start-up Grant Nos.39837137,39837101 and 3827401739)for financial support。
文摘Pyridyl-based ketones and 1,6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products,pharmaceuticals,organic materials and fine chemicals.In this context,we herein demonstrate an unprecedented,robust and generally applicable synthetically strategy to deliver these two crucial ketone frameworks via visible-light-induced ring-opening coupling reactions of cycloalcohols with vinylazaarenes and enones,respectively.A plausible mechanism involves the selectiveβ-C-C bond cleavage of cycloalcohols enabled by proton-coupled electron transfer and ensuing Giese-type addition followed by single electron reduction and protonation.The synthetic methodology exhibits broad substrate scope,excellent functional group compatibility as well as operational simplicity and environmental friendliness.
基金financially supported by the National Key Research and Development Program of China(No.2023YFD2200505)the National Natural Science Foundation of China(No.22202105)+3 种基金the Natural Science Foundation of Jiangsu Higher Education Institutions of China(No.21KJA150003)the Innovation and Entrepreneurship Team Program of Jiangsu Province(No.JSSCTD202345)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX23_1163)the China Postdoctoral Science Foundation(Nos.2023M731703 and 2024T170415)
文摘The oxidation of lignin model compounds to esters via C-C bond cleavage has attracted considerable attention,as esters could be used as important polymer precursors and pharmaceutical intermediates.However,most studies focus on designing homogeneous or noble metal catalysts and conducting the reactions under basic conditions.Here,we report an efficient process for the C-C bond cleavage of lignin model compounds and selectively producing esters over different shaped CeO_(2)(i.e.,nanospheres(S),nanorods(R),nanoparticles(P),and nanocubes(C))under base-free conditions.Specifically,the yield of methyl anisate from the aerobic oxidation of l-(4-methoxyphenyl)ethanol reaches 77.6%over CeO_(2)-S in one hour(91%in 9 h),exhibiting higher performance compared to other evaluated CeO_(2)catalysts(6.4%-40.2%).Extensivecharacterizations and experimental investigations reveal that the density of weak base sites and oxygen vacancies on the CeO_(2)surface is positively correlated with the yield of methyl esters.Furthermore,the reaction pathway is investigated,which confirms that 1-(4-methoxyphenyl)ethanol first undergoes two reactions(i.e.,etherification and dehydrogenation)to produce intermediates of1-methoxy-4-(1-methoxy-ethyl)-benzene and 1-(4-methoxyphenyl)ethanone,respectively,followed by a series of functional group transformations to generate the targeted methyl anisate ultimately.
基金financial support from the National Natural Science Foundation of China(Nos.22001147,22371171)Taishan Scholars Project of Shandong Province(No.tsqn202103027)+1 种基金Distinguished Young Scholars of Shandong Province(Overseas)(No.2022HWYQ-001)Qilu Youth Scholar Funding of Shandong University。
文摘The carbon-carbon bond is the one of the most fundamental and abundant bonds that exist in organic molecules,and the challenge of functionalization of carbon-carbon bond has always been a critical pursuit in organic synthesis.In recent years,there have been a growing number of studies on the C-C bond activation.Nevertheless,the metal-catalyzed cleavage of the C-C(O)bond in unstrained ketones has remained relatively underexplored due to the strong affinity of carbonyl groups for metals.In this study,we report a nickel-catalyzed strategy for the reductive alkynylation of ketoimines viaβ-carbon elimination.This method involves the conversion of aryl ketones into aryl ketoimines,thus expanding the toolbox of aryl electrophiles.The use of a N-heterocyclic carbene(NHC)ligand is crucial for this catalytic transformation.This discovery leads to a cross electrophile coupling reaction characterized by its operational simplicity,unique chemo-selectivity and excellent functional group tolerance.In addition,the approach has been effectively applied to the late-stage alkynylation of diverse pharmaceuticals.Ultimately,a series of comprehensive experiments and theoretical studies were conducted to provide insights into the reaction pathway,which supports the proposedβ-carbon elimination process.
文摘Copper(Cu)-based catalysts show significant potential for producing high value-added C_(2+)products in electrocatalytic CO_(2)/CO reduction reactions(CO(2)RR).However,the structural reconfiguration during operation poses substantial challenges in identifying the intrinsic catalytic active site,especially under similar mass transport conditions.Herein,three typical and commercial Cu-based catalysts(Cu,CuO,and Cu_(2)O)are chosen as representatives to elucidate the structure-activity relationship of CORR in the membrane electrode assembly electrolyzer.Notably,only the Cu catalyst demonstrates the most suppression of hydrogen evolution reaction,thus achieving the highest FE of 86.7% for C_(2+)products at a current density of 500 mA cm^(-2) and maintaining a stable electrolysis over 110 h at a current of 200 mA cm^(-2).The influence of chemical valence state of Cu,electrochemical surface area,and local pH were firstly investigated and ruled out for the significant FE differences.Finally,based on the structure analysis from high resolution transmission electron microscope,OH-adsorption,in situ infrared spectroscopy and density functional theory calculations,it is suggested that the asymmetric C-C coupling(via ^(*)CHO and ^(*)CO)is the most probable reaction pathway for forming C_(2+)products,with Cu(100)-dominant grain boundaries(GBs)being the most favorable active sites.These findings provide deeper insights into the synergistic relationship between crystal facets and GBs in electrocatalytic systems.
