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
The transition metal-catalyzed C–H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step-and atom-economy,the abundan...The transition metal-catalyzed C–H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step-and atom-economy,the abundance of hydrocarbon compounds,and the potential for late-stage functionalization of complex organic molecules.The ortho-and meta-C-H activation and functionalization of aromatic compounds have been widely explored in recent years,however the distal para-C-H activation and functionalization has remained a significant challenge because of the difficulty in forming energetically favorable metallacyclic transition states.The utilization of appropriate directing groups or templates as well as the meticulous design of catalysts and ligands has proven to be effective in transition-metal-catalyzed remote para-C-H bonds activation and functionalization of aromatic compounds.This review aims to summarize the strategies for controlling para-selective C–H functionalization using the directing group,template engineering,and catalyst/ligand design under transition metals catalysis in recent years.展开更多
Silver-catalyzed decarboxylative C–H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been realized under mild reaction conditions generating the corresponding products in moderate to good ...Silver-catalyzed decarboxylative C–H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been realized under mild reaction conditions generating the corresponding products in moderate to good yields(32%–91%).In addition,a gram-scale reaction,late-stage modification of drug,synthetic transformation of the product,and further application of the catalytic strategy were also performed.Preliminary studies indicate that the reaction undergoes a radical process.展开更多
We reported the characterization of a novel brassicicene diterpene biosynthetic gene cluster,which contains a uniqueα-ketoglutarate-dependent dioxygenase(αKGD)enzyme,AbnI.Our findings revealed that AbnI demonstrates...We reported the characterization of a novel brassicicene diterpene biosynthetic gene cluster,which contains a uniqueα-ketoglutarate-dependent dioxygenase(αKGD)enzyme,AbnI.Our findings revealed that AbnI demonstrates remarkable substrate promiscuity and is capable of activating multiple sites on both 5-8-5 and 5-9-5 brassicicene skeletons,resulting in skeleton modifications and an unexpected ring system rearrangement.These results suggested the potential utility of AbnI as an enzymatic tool for terpene C-H functionalization.In addition,the catalytic mechanism of AbnI and its potential ecological implications were discussed.展开更多
(S,S)-Me-BI-DIME/Pd(0)-catalyzed ennantioselective C-H functionalization of N-ferrocenyl o-bromobenzanilides has been realized,affording isoquinolinone-fused ferrocenes with up to 97% ee.The products can be transforme...(S,S)-Me-BI-DIME/Pd(0)-catalyzed ennantioselective C-H functionalization of N-ferrocenyl o-bromobenzanilides has been realized,affording isoquinolinone-fused ferrocenes with up to 97% ee.The products can be transformed into planar chiral ferrocenyl monophosphines,which demonstrate their preliminary application.展开更多
Late-stage modification of peptides and proteins meets the increasing demand in biochemical and pharmaceutical communities. These modification strategies could provide functionalized nonproteinogenic analogues with en...Late-stage modification of peptides and proteins meets the increasing demand in biochemical and pharmaceutical communities. These modification strategies could provide functionalized nonproteinogenic analogues with enhanced biological activities or improved therapeutic capabilities compared to their natural counterparts. Recent years, transition-metal-promoted functionalization of ubiquitous C-H bonds has been emerged as a powerful and tunable tool in this area, both for backbone diversifications and labeling of specific moieties. These reactions were flexible and expedient in both academic and industrial laboratories, especially considering their atom and step-economy, good functional group compatibility, accurate site selectivity. This review surveys the progress achieved in the late-stage modification of peptides and proteins utilizing transition-metal-catalyzed C-H functionalization with C-C and C-X(F, Cl, O, N, B, etc.) bonds formation.展开更多
The new reactions between o-hydroxyphenyl enaminones and Langlois reagent(CF_(3)SO_(2)Na)for the tunable synthesis of 3-(trifluoromethylthio)chromones and 3-trifluoromethylsulfinyl chromones are reported herein.Both t...The new reactions between o-hydroxyphenyl enaminones and Langlois reagent(CF_(3)SO_(2)Na)for the tunable synthesis of 3-(trifluoromethylthio)chromones and 3-trifluoromethylsulfinyl chromones are reported herein.Both type of reactions proceed under transition metal-free conditions.In addition,the conditions for the synthesis of 3-trifluoromethylsulfinyl chromones have also been found to be applicable for the synthesis of 3-alkyl/arylsulfinyl chromones.展开更多
Palladium-catalyzed non-directed C-H functionalization provides an efficient approach for direct functionalization of arenes, but it usually suffers from poor site selectivity, limiting its wide application.Herein, it...Palladium-catalyzed non-directed C-H functionalization provides an efficient approach for direct functionalization of arenes, but it usually suffers from poor site selectivity, limiting its wide application.Herein, it is reported for the first time that the carboxylic acid ligand of 3,5-dimethyladamantane-1-carboxylic acid(1-DMAd CO_(2)H) can affect the site selectivity during the C-H activation step in palladiumcatalyzed non-directed C-H functionalization, leading to highly para-selective C-H olefination of TIPSprotected phenols. This transformation displayed good generality in realizing various other para-selective C-H functionalization reactions such as halogenation, and allylation reactions. A wide variety of phenol derivatives including bioactive molecules of triclosan, thymol, and propofol, were compatible substrates,leading to the corresponding para-selective products in moderate to good yields. A preliminary mechanism study revealed that the spatial repulsion factor between carboxylic acid ligand and bulky protecting group resulted in the selective C-H activation at the less sterically hindered para-position. This new model non-directed para-selective C-H functionalization can provide a straightforward route for remote site-selective C-H activations.展开更多
A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4+3]annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time,and used to produce a range of hitherto unreport...A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4+3]annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time,and used to produce a range of hitherto unreported precedentedβ-monofluorinated benzo[b]azepin-5-ones with good yields and complete regioselectivity.This approach features a broad substrate scope,good functional group tolerance,and high regioselectivity,which may include Rh(Ⅲ)-catalyzed aldehydic C-H activation,tandem site-/regioselective insertion,defluorinated ring-scission,and 1,2-elimination.展开更多
Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry,significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access thi...Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry,significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold.Catalyzed direct Csp^(2)-H functionalization provides an effective and costefficient approach to synthesizing carbazoles from simple and readily available starting materials,ensuring a promising path characterized by excellent atom and step economy.This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp^(2)-H functionalization techniques for synthesizing carbazoles.展开更多
Although rare-earth-catalysed C-H addition to unsaturated hydrocarbons has emerged as a powerful and atom-economical strategy,the mechanistic principles governing selectivity in reactions involving conjugated dienes r...Although rare-earth-catalysed C-H addition to unsaturated hydrocarbons has emerged as a powerful and atom-economical strategy,the mechanistic principles governing selectivity in reactions involving conjugated dienes remain poorly understood.Here,density functional theory(DFT)calculations are employed to elucidate the mechanistic origins of divergent selectivity in rare-earth-catalysed pyridine C-H alkylation and aldimine annulation reactions with conjugated dienes.The results indicate that,despite producing formal 1,4-and 1,2-insertion products,respectively,both transformations proceed through a preferred 1,4-cis-insertion pathway to generate η^(3)-allyl intermediates.Comprehensive computational analyses reveal that the divergence arises from distinct post-insertion pathways:sterically favored protonation at the terminal carbon in pyridine alkylation,versus electronically and sterically driven cyclization at the internal carbon in aldimine annulation.These results demonstrate that product selectivity is dictated primarily by the site-selective evolution of the η^(3)-allyl intermediate rather than by the initial insertion event.This work establishes a unified mechanistic framework for diene-enabled rare-earth-catalysed C-H functionalization and provides theoretical insights into selectivity control through post-insertion reactivity.展开更多
The topic of C-H functionalization and C-O formation is the most important area in organic synthesis.Traditional methods are very limited due to the necessary external oxidants,whereas the rapidly developing electroch...The topic of C-H functionalization and C-O formation is the most important area in organic synthesis.Traditional methods are very limited due to the necessary external oxidants,whereas the rapidly developing electrochemical synthesis uses electrons as internal redox reagents.Consequently,electrochemical C-H functionalization for the construction of C-O bonds has emerged as an active area of research.This review categorizes recent reports on the electrochemical formation of C-O bonds with various C-H sources based on the hybridization(sp^(3),sp^(2))of the carbon atoms involved.Potential readers will gain a more comprehensive understanding of advances in the field through this review.展开更多
The development of C-H functionalization methods for directly converting C-H bonds into C-C bonds has drawn significant attention.These reactions typically require the concurrent involvement of distinct catalytic proc...The development of C-H functionalization methods for directly converting C-H bonds into C-C bonds has drawn significant attention.These reactions typically require the concurrent involvement of distinct catalytic processes,such as photoredox and transition metal catalysis.Combining the corresponding catalytic sites within a single catalyst,instead of adding extra cocatalysts,remains a significant challenge.Here,we present a novel pyridone-based hydrogen-bonded organic framework(HOF),named PFC-943,which exhibits exceptional visible-light absorption properties while integrating both photosensitizing and redox-active sites within its skeleton.Femtosecond transient absorption spectroscopy(fs-TA)reveals that the excited-state electrons of PFC-943 in ethanol exhibit an extended lifetime.Leveraging this unique excited-state electron behavior,PFC-943converts oxygen into highly reactive singlet oxygen(^(1)O_(2))via an energy transfer(En T)pathway and facilitates a key carbanion intermediate through a single electron transfer(SET)process.Consequently,the metal-free PFC-943 exhibits remarkable photocatalytic performance in C-H bond arylation reaction of quinoxalin-2(1H)-one.This work presents the first dual-functional HOF for radical-mediated C-H functionalization reactions,offering a novel approach to C-H bond functionalization.展开更多
Nickel-catalyzed borylation of aryl nonaflates with B2pin2 could be realized,which proceeded effectively by means of C—O bond functionalization to afford a wide variety of valuable arylboronates in moderate to excell...Nickel-catalyzed borylation of aryl nonaflates with B2pin2 could be realized,which proceeded effectively by means of C—O bond functionalization to afford a wide variety of valuable arylboronates in moderate to excellent yields with good functionality compatibility.In addition,the gram-scale synthesis and the application of the approach in the late-stage elaboration of aryl nonaflate derived from pterostilbene could also be achieved.展开更多
Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/...Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/chemical stability.To enhance the performance of intrinsic g-CN,a supramolecular self-assembly strategy has been proposed to regulate the molecular structure of supramolecular precursors through non-covalent interactions across molecular building blocks,thereby optimizing the electronic structure of g-CN.This review provides a comprehensive overview of the recent progress in supramolecular self-assembly-derived graphitic carbon nitride(SM-CN)from both experimental and theoretical computational research in synthesis strategies,including synthesis methods and influencing factors,providing a theoretical foundation for the design of supramolecular assembly.It also discusses modification strategies,such as internal modification of the conjugated plane,interlayer optimization,and construction of heterointerfaces to improve the electronic structure of SM-CN owing to its unique layered structure.This review further summarizes the applications of SM-CN in environment and energy,including wastewater treatment,sterilization and disinfection/air purification,water splitting,H_(2)O_(2)production,organic synthesis/biomass conversion,CO_(2)reduction,photocatalytic coupling technology.Finally,perspectives and outlooks for the future development of SM-CN aim to inspire further innovation in the design and construction of high-performance SM-CN for broader applications.展开更多
Aerogels,renowned as ultra-lightweight solids with exceptional porosity and specific surface area,have emerged as pivotal materials for thermal insulation,catalysis,energy storage,and biomedicine.This review comprehen...Aerogels,renowned as ultra-lightweight solids with exceptional porosity and specific surface area,have emerged as pivotal materials for thermal insulation,catalysis,energy storage,and biomedicine.This review comprehensively evaluates the recent strides in sustainable,high-performance cellulose-based aerogels,emphasizing their fabrication,functionalization,and application prospects.It details the extraction of cellulose fromdiverse sources and its subsequent processing into nanocellulose(e.g.,cellulose nanofibrils and nanocrystals),which serves as the fundamental building block for aerogel synthesis.The critical sol-gel transition,solvent selection,and the pivotal role of drying techniques—freeze-drying,supercritical drying,and ambient pressure drying—in determining final aerogel architecture and properties are systematically analyzed.Special emphasis is placed on the advanced chemical modification of nanocellulose,including esterification,click chemistry,etherification,silanization,and amidation,which tailors surface chemistry to impart hydrophobicity,reactivity,or specific binding sites.The profound influence of cellulose source characteristics(aspect ratio,crystallinity,surface charge)on the pore-forming mechanism and aerogel performance is thoroughly discussed,bridging raw material selection with microstructure design.The review further elucidates the engineering of hybrid and composite aerogels by integrating silica,graphene,polymers,semiconductors,and metal-organic frameworks(MOFs),which synergistically enhance functionalities for targeted applications such as adsorption,photocatalysis,energy storage,sensing,and biomedical engineering.Despite significant progress,challenges remain in scalable green fabrication,balancing ultra-high porosity with mechanical robustness,and deepening the mechanistic understanding in complex applications.This work consolidates the current state-of-the-art,identifies key knowledge gaps,and provides a forward-looking perspective on the development of cellulose aerogels as versatile platforms for next-generation sustainable technologies.展开更多
Vanadium-based materials have emerged as promising cathode candidates for aqueous zinc-ion batteries(AZIBs)due to their multivalent redox characteristics and diverse crystal structures,which enable high energy storage...Vanadium-based materials have emerged as promising cathode candidates for aqueous zinc-ion batteries(AZIBs)due to their multivalent redox characteristics and diverse crystal structures,which enable high energy storage capacity.Nevertheless,practical applications are hindered by several critical challenges,including vanadium species dissolution,side-product formation,sluggish Zn^(2+)diffusion kinetics,and low electrical conductivity.Organic functionalization,benefiting from its structural tunability and abundant functional groups,has been proven to be an effective strategy for enhancing the electrochemical performance of vanadium-based cathodes.This review systematically summarizes recent advances in organic-functionalized vanadium-based cathodes.First,the energy storage mechanism of vanadiumbased cathodes and the fundamental properties of organic compounds relevant to cathode optimization are outlined.Then,the functions of organic compounds are comprehensively analyzed from four key perspectives:capacity improvement,conductivity enhancement,Zn^(2+)diffusion kinetics optimization,and cycling stability promotion.Furthermore,the specific electrochemical performance modulation effects and practical application examples of this strategy are discussed in detail.Finally,current limitations and challenges in this field are highlighted,and corresponding solutions and future research directions are proposed,offering theoretical guidance and insights for the development of high-performance vanadium-based cathodes for AZIBs.展开更多
Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous struct...Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous structure and intrinsic lithiophilic property.In this work,we introduce interface-engineered cellulose-based separators by converting intrinsic hydroxyl groups on cellulose nanofibers(CNFs)to nitrogen functionalities through a trace conducting polymer coating.Both experimental and theoretical results reveal that the nitrogen moieties disrupt the compact hydrogen bond network within hydroxyl cellulose,enabling multiple nitrogen-lithium interactions that enhance lithium ion transport.In addition to an extraordinary Li^(+)transference number of 0.86 and a high ionic conductivity of 1.1 mS cm^(-1),the nitrogen-functionalized CNF contributes to a uniform electric field and Li^(+)concentration distribution across the lithium metal surface.This facilitates the formation of a LiF-rich solid electrolyte interface and suppresses Li dendrite growth.Consequently,Li‖Li cells demonstrate stable plating/stripping cycles for approximately 3000 h at a current density of 1 mA cm^(-2) with a fixed capacity of 1 mAh cm^(-2),while maintaining a low overpotential of 15 mV.Our work provides valuable insights into the surface functionalization of natural biomass for advancing sustainable energy storage technologies.展开更多
Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal ...Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.展开更多
Quinoxalin-2(1H)-ones are unique nitrogen-containing organic compounds with wide applications in the agrochemical,pharmaceutical,and chemical industries as well as in material science.During the last decades,visible-l...Quinoxalin-2(1H)-ones are unique nitrogen-containing organic compounds with wide applications in the agrochemical,pharmaceutical,and chemical industries as well as in material science.During the last decades,visible-light-promoted photoredox catalysis has emerged as a versatile platform for constructing quinoxalin-2(1H)-one scaffolds under exceptionally mild conditions.In this review,we provide an overview of recent advances in photocatalytic direct C(3)–H functionalization of quinoxaline-2(1H)-ones,including the construction of C(3)–C bonds and C(3)–R_(F)/C/O/N/Cl/S/D bonds,as well as the related reaction mechanisms.We aim to enhance the methods for the reaction of quinoxalin-2(1H)-ones at the C-3 position,which have extensive applications in organic synthesis and medicinal chemistry.展开更多
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.
基金support from the National Natural Science Foundation of China(No.21901206)Postdoctoral Science Foundation of China(No.2022M712589)+2 种基金General Key R&D Projects in Shaanxi Province(No.2023-YBGY-321)Natural Science Foundation of Chongqing(No.CSTB2022NSCQ-MSX0826)National&Local Joint Engineering Research Center for mineral Salt Deep Utilization,Huaiyin Institute of Technology(No.SF202407)for financial support。
文摘The transition metal-catalyzed C–H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step-and atom-economy,the abundance of hydrocarbon compounds,and the potential for late-stage functionalization of complex organic molecules.The ortho-and meta-C-H activation and functionalization of aromatic compounds have been widely explored in recent years,however the distal para-C-H activation and functionalization has remained a significant challenge because of the difficulty in forming energetically favorable metallacyclic transition states.The utilization of appropriate directing groups or templates as well as the meticulous design of catalysts and ligands has proven to be effective in transition-metal-catalyzed remote para-C-H bonds activation and functionalization of aromatic compounds.This review aims to summarize the strategies for controlling para-selective C–H functionalization using the directing group,template engineering,and catalyst/ligand design under transition metals catalysis in recent years.
基金financially supported by the National Natural Science Foundation of China(Nos.21402116,21502111,21572126)the Science and Technology Innovation Talents of Henan Province(No.2018JQ0011)the Key Science Research of Education Committee in Henan Province(No.21A150044)。
文摘Silver-catalyzed decarboxylative C–H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been realized under mild reaction conditions generating the corresponding products in moderate to good yields(32%–91%).In addition,a gram-scale reaction,late-stage modification of drug,synthetic transformation of the product,and further application of the catalytic strategy were also performed.Preliminary studies indicate that the reaction undergoes a radical process.
基金financially supported by the National Key R&D Program of China(Nos.2021YFA0910500,2021YFA0910503)the National Natural Science Foundation of China(Nos.22277035,32000045 and 81973205)+4 种基金the Program for Changjiang Scholars of Ministry of Education of the People’s Republic of China(No.T2016088)the National Natural Science Foundation for Distinguished Young Scholars(No.81725021)the National Science and Technology Project of China(No.2018ZX09201001-001-003)Innovative Research Groups of the National Natural Science Foundation of China(No.81721005)the Fundamental Research Funds for the Central Universities(No.2020kfyXJJS043).
文摘We reported the characterization of a novel brassicicene diterpene biosynthetic gene cluster,which contains a uniqueα-ketoglutarate-dependent dioxygenase(αKGD)enzyme,AbnI.Our findings revealed that AbnI demonstrates remarkable substrate promiscuity and is capable of activating multiple sites on both 5-8-5 and 5-9-5 brassicicene skeletons,resulting in skeleton modifications and an unexpected ring system rearrangement.These results suggested the potential utility of AbnI as an enzymatic tool for terpene C-H functionalization.In addition,the catalytic mechanism of AbnI and its potential ecological implications were discussed.
基金the financial support from the National Natural Science Foundation of China(Nos.21572126,21202095,14HASTIT016)Technicians Troop Construction Projects of Henan Province(No.C20150030)Program of Science and Technology Innovation Talents of Henan Province(No.184100510011)。
文摘(S,S)-Me-BI-DIME/Pd(0)-catalyzed ennantioselective C-H functionalization of N-ferrocenyl o-bromobenzanilides has been realized,affording isoquinolinone-fused ferrocenes with up to 97% ee.The products can be transformed into planar chiral ferrocenyl monophosphines,which demonstrate their preliminary application.
基金the support from the National Key R&D Program of China(No. 2017YFA0505400)the National Natural Science Foundation of China (Nos. 21572214, 21702200)
文摘Late-stage modification of peptides and proteins meets the increasing demand in biochemical and pharmaceutical communities. These modification strategies could provide functionalized nonproteinogenic analogues with enhanced biological activities or improved therapeutic capabilities compared to their natural counterparts. Recent years, transition-metal-promoted functionalization of ubiquitous C-H bonds has been emerged as a powerful and tunable tool in this area, both for backbone diversifications and labeling of specific moieties. These reactions were flexible and expedient in both academic and industrial laboratories, especially considering their atom and step-economy, good functional group compatibility, accurate site selectivity. This review surveys the progress achieved in the late-stage modification of peptides and proteins utilizing transition-metal-catalyzed C-H functionalization with C-C and C-X(F, Cl, O, N, B, etc.) bonds formation.
基金financially supported by National Natural Science Foundation of China(No.22161022)。
文摘The new reactions between o-hydroxyphenyl enaminones and Langlois reagent(CF_(3)SO_(2)Na)for the tunable synthesis of 3-(trifluoromethylthio)chromones and 3-trifluoromethylsulfinyl chromones are reported herein.Both type of reactions proceed under transition metal-free conditions.In addition,the conditions for the synthesis of 3-trifluoromethylsulfinyl chromones have also been found to be applicable for the synthesis of 3-alkyl/arylsulfinyl chromones.
基金supported by the National Natural Science Foundation of China(No.21772139)the Jiangsu Province Natural Science Found for Distinguished Young Scholars(No.BK20180041)+1 种基金the PAPD Projectsupported by the Open Research Fund of the School of Chemistry and Chemical Engineering,Henan Normal University。
文摘Palladium-catalyzed non-directed C-H functionalization provides an efficient approach for direct functionalization of arenes, but it usually suffers from poor site selectivity, limiting its wide application.Herein, it is reported for the first time that the carboxylic acid ligand of 3,5-dimethyladamantane-1-carboxylic acid(1-DMAd CO_(2)H) can affect the site selectivity during the C-H activation step in palladiumcatalyzed non-directed C-H functionalization, leading to highly para-selective C-H olefination of TIPSprotected phenols. This transformation displayed good generality in realizing various other para-selective C-H functionalization reactions such as halogenation, and allylation reactions. A wide variety of phenol derivatives including bioactive molecules of triclosan, thymol, and propofol, were compatible substrates,leading to the corresponding para-selective products in moderate to good yields. A preliminary mechanism study revealed that the spatial repulsion factor between carboxylic acid ligand and bulky protecting group resulted in the selective C-H activation at the less sterically hindered para-position. This new model non-directed para-selective C-H functionalization can provide a straightforward route for remote site-selective C-H activations.
基金financial support from the schoollevel research projects of Yancheng Institute of Technology(No.xjr2020044)the National Natural Science Foundation of China(Nos.22101151 and 21971090)。
文摘A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4+3]annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time,and used to produce a range of hitherto unreported precedentedβ-monofluorinated benzo[b]azepin-5-ones with good yields and complete regioselectivity.This approach features a broad substrate scope,good functional group tolerance,and high regioselectivity,which may include Rh(Ⅲ)-catalyzed aldehydic C-H activation,tandem site-/regioselective insertion,defluorinated ring-scission,and 1,2-elimination.
基金support and funding by the European Union-Next Generation EU under the Italian Ministry of University and Research (MUR) National Innovation Ecosystem (No.ECS00000041-VITALITY and also “Ecosistema TECH4YOU-(Spoke 3-Goal 3.5)MUR is thanked for PRIN-PNRR 2022 project "P2022XKWH7-Circular Waste+3 种基金The University of Perugia is acknowledged for financial support to the university project “Fondo Ricerca di Ateneo,edizione 2022”The National Ph D program in Catalysis coordinated by the University of Perugia is also thankedthe financial supports of key research and development and technology transfer projects of Inner Mongolia Autonomous Region (No.2025KJHZ0008)major special projects of science and technology of Ordos (No.2022EEDSKJZDZX003)。
文摘Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry,significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold.Catalyzed direct Csp^(2)-H functionalization provides an effective and costefficient approach to synthesizing carbazoles from simple and readily available starting materials,ensuring a promising path characterized by excellent atom and step economy.This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp^(2)-H functionalization techniques for synthesizing carbazoles.
基金supported by National Natural Science Foundation of China(no.22522101,22271001,22003001).
文摘Although rare-earth-catalysed C-H addition to unsaturated hydrocarbons has emerged as a powerful and atom-economical strategy,the mechanistic principles governing selectivity in reactions involving conjugated dienes remain poorly understood.Here,density functional theory(DFT)calculations are employed to elucidate the mechanistic origins of divergent selectivity in rare-earth-catalysed pyridine C-H alkylation and aldimine annulation reactions with conjugated dienes.The results indicate that,despite producing formal 1,4-and 1,2-insertion products,respectively,both transformations proceed through a preferred 1,4-cis-insertion pathway to generate η^(3)-allyl intermediates.Comprehensive computational analyses reveal that the divergence arises from distinct post-insertion pathways:sterically favored protonation at the terminal carbon in pyridine alkylation,versus electronically and sterically driven cyclization at the internal carbon in aldimine annulation.These results demonstrate that product selectivity is dictated primarily by the site-selective evolution of the η^(3)-allyl intermediate rather than by the initial insertion event.This work establishes a unified mechanistic framework for diene-enabled rare-earth-catalysed C-H functionalization and provides theoretical insights into selectivity control through post-insertion reactivity.
基金supported by the National Natural Science Foundation of China(No.22101299)Chinese Universities Scientific Fund(No.2025TC055)Central University Guided Funds for Building World-Class Universities(Disciplines)and Advancing Characteristic Development.
文摘The topic of C-H functionalization and C-O formation is the most important area in organic synthesis.Traditional methods are very limited due to the necessary external oxidants,whereas the rapidly developing electrochemical synthesis uses electrons as internal redox reagents.Consequently,electrochemical C-H functionalization for the construction of C-O bonds has emerged as an active area of research.This review categorizes recent reports on the electrochemical formation of C-O bonds with various C-H sources based on the hybridization(sp^(3),sp^(2))of the carbon atoms involved.Potential readers will gain a more comprehensive understanding of advances in the field through this review.
基金supported by the Natural Science Foundation of Fujian Province(2024J010040 and 2024J09054)the Chinese Academy of Sciences Youth Interdisciplinary Team(JCTD-2022-12)the National Natural Science Foundation of China(22272178)。
文摘The development of C-H functionalization methods for directly converting C-H bonds into C-C bonds has drawn significant attention.These reactions typically require the concurrent involvement of distinct catalytic processes,such as photoredox and transition metal catalysis.Combining the corresponding catalytic sites within a single catalyst,instead of adding extra cocatalysts,remains a significant challenge.Here,we present a novel pyridone-based hydrogen-bonded organic framework(HOF),named PFC-943,which exhibits exceptional visible-light absorption properties while integrating both photosensitizing and redox-active sites within its skeleton.Femtosecond transient absorption spectroscopy(fs-TA)reveals that the excited-state electrons of PFC-943 in ethanol exhibit an extended lifetime.Leveraging this unique excited-state electron behavior,PFC-943converts oxygen into highly reactive singlet oxygen(^(1)O_(2))via an energy transfer(En T)pathway and facilitates a key carbanion intermediate through a single electron transfer(SET)process.Consequently,the metal-free PFC-943 exhibits remarkable photocatalytic performance in C-H bond arylation reaction of quinoxalin-2(1H)-one.This work presents the first dual-functional HOF for radical-mediated C-H functionalization reactions,offering a novel approach to C-H bond functionalization.
文摘Nickel-catalyzed borylation of aryl nonaflates with B2pin2 could be realized,which proceeded effectively by means of C—O bond functionalization to afford a wide variety of valuable arylboronates in moderate to excellent yields with good functionality compatibility.In addition,the gram-scale synthesis and the application of the approach in the late-stage elaboration of aryl nonaflate derived from pterostilbene could also be achieved.
基金supported by the National Natural Science Foundation of China(NSFC No.52271228)the Natural Science Foundation of Shaanxi Province(No.2023-JC-ZD-21)the Doctoral Dissertation Innovation Fund of Xi'an University of Technology(No.101-252072301)。
文摘Graphitic carbon nitride(g-CN)stands out as the most promising candidate for solar energy conversion owing to its easy preparation,metal-free nature,flexible molecular structure,moderate bandgap,and excellent thermal/chemical stability.To enhance the performance of intrinsic g-CN,a supramolecular self-assembly strategy has been proposed to regulate the molecular structure of supramolecular precursors through non-covalent interactions across molecular building blocks,thereby optimizing the electronic structure of g-CN.This review provides a comprehensive overview of the recent progress in supramolecular self-assembly-derived graphitic carbon nitride(SM-CN)from both experimental and theoretical computational research in synthesis strategies,including synthesis methods and influencing factors,providing a theoretical foundation for the design of supramolecular assembly.It also discusses modification strategies,such as internal modification of the conjugated plane,interlayer optimization,and construction of heterointerfaces to improve the electronic structure of SM-CN owing to its unique layered structure.This review further summarizes the applications of SM-CN in environment and energy,including wastewater treatment,sterilization and disinfection/air purification,water splitting,H_(2)O_(2)production,organic synthesis/biomass conversion,CO_(2)reduction,photocatalytic coupling technology.Finally,perspectives and outlooks for the future development of SM-CN aim to inspire further innovation in the design and construction of high-performance SM-CN for broader applications.
基金funded by Basic Scientific Research Funds Project of Heilongjiang Universities of Department of Education,Heilongjiang Province,China,grant number 2025-KYYWF-ZR0763.
文摘Aerogels,renowned as ultra-lightweight solids with exceptional porosity and specific surface area,have emerged as pivotal materials for thermal insulation,catalysis,energy storage,and biomedicine.This review comprehensively evaluates the recent strides in sustainable,high-performance cellulose-based aerogels,emphasizing their fabrication,functionalization,and application prospects.It details the extraction of cellulose fromdiverse sources and its subsequent processing into nanocellulose(e.g.,cellulose nanofibrils and nanocrystals),which serves as the fundamental building block for aerogel synthesis.The critical sol-gel transition,solvent selection,and the pivotal role of drying techniques—freeze-drying,supercritical drying,and ambient pressure drying—in determining final aerogel architecture and properties are systematically analyzed.Special emphasis is placed on the advanced chemical modification of nanocellulose,including esterification,click chemistry,etherification,silanization,and amidation,which tailors surface chemistry to impart hydrophobicity,reactivity,or specific binding sites.The profound influence of cellulose source characteristics(aspect ratio,crystallinity,surface charge)on the pore-forming mechanism and aerogel performance is thoroughly discussed,bridging raw material selection with microstructure design.The review further elucidates the engineering of hybrid and composite aerogels by integrating silica,graphene,polymers,semiconductors,and metal-organic frameworks(MOFs),which synergistically enhance functionalities for targeted applications such as adsorption,photocatalysis,energy storage,sensing,and biomedical engineering.Despite significant progress,challenges remain in scalable green fabrication,balancing ultra-high porosity with mechanical robustness,and deepening the mechanistic understanding in complex applications.This work consolidates the current state-of-the-art,identifies key knowledge gaps,and provides a forward-looking perspective on the development of cellulose aerogels as versatile platforms for next-generation sustainable technologies.
基金financial support from the National Natural Science Foundation of China(No.21676036)the Natural Science Foundation of Chongqing(No.CSTB2023NSCQMSX0580)the Large-scale Equipment Sharing Fund of Chongqing University(No.202403150240 and 202503150091)。
文摘Vanadium-based materials have emerged as promising cathode candidates for aqueous zinc-ion batteries(AZIBs)due to their multivalent redox characteristics and diverse crystal structures,which enable high energy storage capacity.Nevertheless,practical applications are hindered by several critical challenges,including vanadium species dissolution,side-product formation,sluggish Zn^(2+)diffusion kinetics,and low electrical conductivity.Organic functionalization,benefiting from its structural tunability and abundant functional groups,has been proven to be an effective strategy for enhancing the electrochemical performance of vanadium-based cathodes.This review systematically summarizes recent advances in organic-functionalized vanadium-based cathodes.First,the energy storage mechanism of vanadiumbased cathodes and the fundamental properties of organic compounds relevant to cathode optimization are outlined.Then,the functions of organic compounds are comprehensively analyzed from four key perspectives:capacity improvement,conductivity enhancement,Zn^(2+)diffusion kinetics optimization,and cycling stability promotion.Furthermore,the specific electrochemical performance modulation effects and practical application examples of this strategy are discussed in detail.Finally,current limitations and challenges in this field are highlighted,and corresponding solutions and future research directions are proposed,offering theoretical guidance and insights for the development of high-performance vanadium-based cathodes for AZIBs.
基金supported by the National Natural Science Foundation of China(Grant No.22479046,22461142135)。
文摘Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous structure and intrinsic lithiophilic property.In this work,we introduce interface-engineered cellulose-based separators by converting intrinsic hydroxyl groups on cellulose nanofibers(CNFs)to nitrogen functionalities through a trace conducting polymer coating.Both experimental and theoretical results reveal that the nitrogen moieties disrupt the compact hydrogen bond network within hydroxyl cellulose,enabling multiple nitrogen-lithium interactions that enhance lithium ion transport.In addition to an extraordinary Li^(+)transference number of 0.86 and a high ionic conductivity of 1.1 mS cm^(-1),the nitrogen-functionalized CNF contributes to a uniform electric field and Li^(+)concentration distribution across the lithium metal surface.This facilitates the formation of a LiF-rich solid electrolyte interface and suppresses Li dendrite growth.Consequently,Li‖Li cells demonstrate stable plating/stripping cycles for approximately 3000 h at a current density of 1 mA cm^(-2) with a fixed capacity of 1 mAh cm^(-2),while maintaining a low overpotential of 15 mV.Our work provides valuable insights into the surface functionalization of natural biomass for advancing sustainable energy storage technologies.
基金funded by the National Nature Science Foundation of China(62264006,62574102)“Thousand Talents Program”of Yunnan Province for Young Talents,Innovative Research Teams(in Science and Technology)in the University of Yunnan Province(IRTSTYN),XingDian Talent Support Program for Young Talents,and Frontier Research Team of Kunming University 2023,The Basic Research Project of Yunnan Province(Nos.202201AU070022)+2 种基金Kunming University Talent Introduction Fund(Nos.YJL20024)Yunnan Province Education Department Scientific Research Fund Project(Nos.2024Y759)Undergraduate Innovation and Entrepreneurship Training Program Project of Yunnan Provincial(202411393005)。
文摘Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.
基金support from the National Natural Science Foundation of China(No.22101267)the China Postdoctoral Science Foundation(Nos.2021M692905 and 2024T170832)+2 种基金Natural Science Foundation of Henan Province,China(No.242300421123)Scientific Research Project of Hubei Provincial Education Department,China(No.Q20233104)Hubei Provincial Natural Science Foundation,China(No.2024AFB946).
文摘Quinoxalin-2(1H)-ones are unique nitrogen-containing organic compounds with wide applications in the agrochemical,pharmaceutical,and chemical industries as well as in material science.During the last decades,visible-light-promoted photoredox catalysis has emerged as a versatile platform for constructing quinoxalin-2(1H)-one scaffolds under exceptionally mild conditions.In this review,we provide an overview of recent advances in photocatalytic direct C(3)–H functionalization of quinoxaline-2(1H)-ones,including the construction of C(3)–C bonds and C(3)–R_(F)/C/O/N/Cl/S/D bonds,as well as the related reaction mechanisms.We aim to enhance the methods for the reaction of quinoxalin-2(1H)-ones at the C-3 position,which have extensive applications in organic synthesis and medicinal chemistry.
