Electrochemical sensors,with their outstanding sensitivity,excellent selectivity,ease of operation,and lower manufacturing costs,have found widespread applications in fields such as disease diagnosis,environmental mon...Electrochemical sensors,with their outstanding sensitivity,excellent selectivity,ease of operation,and lower manufacturing costs,have found widespread applications in fields such as disease diagnosis,environmental monitoring,and food safety.In the development of sensing materials,metal-organic frameworks(MOFs)have become a research hotspot due to their high specific surface area,tunable pore structures,and high designability.Recently,conductive metal-organic frameworks(CMOFs)have brought innovative opportunities to the field of electrochemical sensing,attributing to their remarkable capabilities in catalysis,electron transport,and signal amplification.This review summarizes the significant progress of CMOFs in the field of electrochemical sensing.Firstly,the design and synthesis strategies for CMOFs used in electrochemical sensing are explored,including enhancing the electrochemical properties of MOFs through precise design of different metal nodes and ligands or via post-synthetic modification techniques,covering Cu-based CMOFs,Ni-based CMOFs,Fe-based CMOFs,and CMOF composites.Furthermore,this article elaborately discusses the breakthrough achievements of electrochemical sensors based on CMOFs in applications such as the determination of inorganic ions,detection of organic pollutants,and recognition of gases and biomolecules,and introduces the principles of electrochemical sensing methods and the role of CMOFs in enhancing the performance of electrochemical sensors.Finally,this review analyzes the main challenges currently faced by CMOFs in the field of electrochemical sensors and offers perspectives on their future development.These challenges mainly include stability,selectivity,production costs,and the realization of their large-scale application.CMOFs provide new ideas and material platforms for the development of electrochemical sensors.As researchers deepen their understanding of their properties and technological advances continue,the application prospects of CMOF-based electrochemical sensors will be even broader.展开更多
Allenylboronates are valuable synthetic building blocks and have garnered significant interest.However,their 1,3-diboyl substituted analogs have not been reported.Herein,we disclosed a novel method for creating 1,3-di...Allenylboronates are valuable synthetic building blocks and have garnered significant interest.However,their 1,3-diboyl substituted analogs have not been reported.Herein,we disclosed a novel method for creating 1,3-diboyl allenes from gem-iododiboron compounds and alkynyl Grignard reagents.The starting materials are initially converted into the corresponding propargylic gem-bis(boronates),which then undergo an intermolecular boryl group transfer to afford 1,3-diboyl allenes,as confirmed by mechanistic studies.This method features good tolerance to steric hindrance and is compatible with a wide variety of functional groups.展开更多
Comprehensive Summary:The divergent synthesis of 2-quinolinones and indolin-3-ones through unprecedented Mo-catalyzed controllable carbonyl deoxygenative coupling and formal deoxygenative N-H insertion reactions was r...Comprehensive Summary:The divergent synthesis of 2-quinolinones and indolin-3-ones through unprecedented Mo-catalyzed controllable carbonyl deoxygenative coupling and formal deoxygenative N-H insertion reactions was reported.By simply changing the molybdenum catalytic conditions,both product categories were produced in generally good yields and with high chemoselectivities from the same starting materials.This strategy was robust,convenient and ready for the rapid construction of diverse product libraries.展开更多
Visible light-induced transformation of CO_(2) and CS_(2) into value-added products has attracted worldwide attention because it mimics nature.In this context,although visible-light-induced direct synthesis of dithioc...Visible light-induced transformation of CO_(2) and CS_(2) into value-added products has attracted worldwide attention because it mimics nature.In this context,although visible-light-induced direct synthesis of dithiocarbamates and carbamates employing SO_(2) and CO_(2) as a C1 source has been reported,all these reactions are limited to the preparation of S-alkyl mono-dithiocarbamates and O-alkyl mono-carbamates.Herein,we report a visible-light photoredox-catalyzed multicomponent reaction of diazosulfonium triflates with amines and CS_(2) or CO_(2).Mechanistic studies indicate that the diazomethyl radicals might be generated as the key intermediates,thus providing a direction for the application of diazomethyl radicals with other radical acceptors.展开更多
A dual catalytic manifold that combines photoredox catalysis and phthalate-catalyzed hydrogen-atom abstraction process has been developed to realize diverse fragmentation-functionalization reactions.Key to success is ...A dual catalytic manifold that combines photoredox catalysis and phthalate-catalyzed hydrogen-atom abstraction process has been developed to realize diverse fragmentation-functionalization reactions.Key to success is photocatalytic generation of tether-tunable distonic radical anions(TDRAs)as proton-coupled electron transfer mediators,enabling polarity-matching-based formation of heteroatom-centered radicals that allows for further controlled exploration of chemical space via C-Cβ-scission.These reactions feature exceptionally broad substrate generality,gram-scale synthesis,potential biocompatibility and late-stage modification of complex molecules,while obviating the use of stoichiometric and often unsafe peroxides in our previous studies.Mechanistic studies support a redox-neutral radical relay pathway enabled by in situ-generated,catalytic TDRAs.展开更多
Comprehensive Summary The implementation of divergent protein engineering on the natural transaminase Vf-ω-TA led to the development of two effective mutants(M2 and M8),enabling the enzymatic synthesis of chiral amin...Comprehensive Summary The implementation of divergent protein engineering on the natural transaminase Vf-ω-TA led to the development of two effective mutants(M2 and M8),enabling the enzymatic synthesis of chiral amine precursors of Rivastigmine and Apremilast,respectively.The evolution of the enzymes was guided by crystal structures and a focused mutagenesis strategy,allowing them to effectively address the challenging ketone substrates with significant steric hindrance.Under the optimized reaction parameters,transamination proceeded smoothly in good conversions and with perfect stereochemical control(>99%ee).These processes utilize inexpensiveα-methylbenzylamine as an amine donor and avoid the continuous acetone removal and costly LDH/GDH/NADH systems.展开更多
Comprehensive Summary Phthalides serve as core structures pervasive in a wide array of natural products and drug molecules,which display a diverse array of biological activities.We report herein a highly efficient dyn...Comprehensive Summary Phthalides serve as core structures pervasive in a wide array of natural products and drug molecules,which display a diverse array of biological activities.We report herein a highly efficient dynamic kinetic resolution of 3-hydroxyphthalides by chiral isothioureas(ITUs)catalyzed asymmetric acylation,facilitating the effective synthesis of a variety of chiral phthalidyl esters with good yields and enantioselectivities.Notably,this reaction features mild reaction conditions,expansive substrate scope as well as good functional group compatibility.In addition,the practicality of this method is underscored by the large-scale synthesis,reduced catalyst loading experiment and the synthesis of the chiral phthalidyl ester prodrug.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22204089,52201281,and22234006)Natural Science Foundation of Shandong Province(No.ZR2023MB016)。
文摘Electrochemical sensors,with their outstanding sensitivity,excellent selectivity,ease of operation,and lower manufacturing costs,have found widespread applications in fields such as disease diagnosis,environmental monitoring,and food safety.In the development of sensing materials,metal-organic frameworks(MOFs)have become a research hotspot due to their high specific surface area,tunable pore structures,and high designability.Recently,conductive metal-organic frameworks(CMOFs)have brought innovative opportunities to the field of electrochemical sensing,attributing to their remarkable capabilities in catalysis,electron transport,and signal amplification.This review summarizes the significant progress of CMOFs in the field of electrochemical sensing.Firstly,the design and synthesis strategies for CMOFs used in electrochemical sensing are explored,including enhancing the electrochemical properties of MOFs through precise design of different metal nodes and ligands or via post-synthetic modification techniques,covering Cu-based CMOFs,Ni-based CMOFs,Fe-based CMOFs,and CMOF composites.Furthermore,this article elaborately discusses the breakthrough achievements of electrochemical sensors based on CMOFs in applications such as the determination of inorganic ions,detection of organic pollutants,and recognition of gases and biomolecules,and introduces the principles of electrochemical sensing methods and the role of CMOFs in enhancing the performance of electrochemical sensors.Finally,this review analyzes the main challenges currently faced by CMOFs in the field of electrochemical sensors and offers perspectives on their future development.These challenges mainly include stability,selectivity,production costs,and the realization of their large-scale application.CMOFs provide new ideas and material platforms for the development of electrochemical sensors.As researchers deepen their understanding of their properties and technological advances continue,the application prospects of CMOF-based electrochemical sensors will be even broader.
基金support for this work was provided by National Natural Science Foundation of China(22471074)Shanghai Frontiers Science Center of Molecule Intelligent Syntheses,and the startup funding from East China Normal University(ECNU).
文摘Allenylboronates are valuable synthetic building blocks and have garnered significant interest.However,their 1,3-diboyl substituted analogs have not been reported.Herein,we disclosed a novel method for creating 1,3-diboyl allenes from gem-iododiboron compounds and alkynyl Grignard reagents.The starting materials are initially converted into the corresponding propargylic gem-bis(boronates),which then undergo an intermolecular boryl group transfer to afford 1,3-diboyl allenes,as confirmed by mechanistic studies.This method features good tolerance to steric hindrance and is compatible with a wide variety of functional groups.
基金financial support from the National Key R&D Program of China(2021YFA1502500)the National Natural Science Foundation of china(22171236 and 22371238).
文摘Comprehensive Summary:The divergent synthesis of 2-quinolinones and indolin-3-ones through unprecedented Mo-catalyzed controllable carbonyl deoxygenative coupling and formal deoxygenative N-H insertion reactions was reported.By simply changing the molybdenum catalytic conditions,both product categories were produced in generally good yields and with high chemoselectivities from the same starting materials.This strategy was robust,convenient and ready for the rapid construction of diverse product libraries.
基金Financial support of this research by the Natural Sciences Foundation of Jilin Province(20240101176JC)National Natural Sciences Foundation of China(21871044)is greatly acknowledged.
文摘Visible light-induced transformation of CO_(2) and CS_(2) into value-added products has attracted worldwide attention because it mimics nature.In this context,although visible-light-induced direct synthesis of dithiocarbamates and carbamates employing SO_(2) and CO_(2) as a C1 source has been reported,all these reactions are limited to the preparation of S-alkyl mono-dithiocarbamates and O-alkyl mono-carbamates.Herein,we report a visible-light photoredox-catalyzed multicomponent reaction of diazosulfonium triflates with amines and CS_(2) or CO_(2).Mechanistic studies indicate that the diazomethyl radicals might be generated as the key intermediates,thus providing a direction for the application of diazomethyl radicals with other radical acceptors.
基金support from the National Natural Science Foundation of China(Nos.22271069,21871067)the Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515012457,2021A1515010190)the Shenzhen Science and Technology Program(Nos.JCYJ20240813105110014 and GXWD20231130100539001).
文摘A dual catalytic manifold that combines photoredox catalysis and phthalate-catalyzed hydrogen-atom abstraction process has been developed to realize diverse fragmentation-functionalization reactions.Key to success is photocatalytic generation of tether-tunable distonic radical anions(TDRAs)as proton-coupled electron transfer mediators,enabling polarity-matching-based formation of heteroatom-centered radicals that allows for further controlled exploration of chemical space via C-Cβ-scission.These reactions feature exceptionally broad substrate generality,gram-scale synthesis,potential biocompatibility and late-stage modification of complex molecules,while obviating the use of stoichiometric and often unsafe peroxides in our previous studies.Mechanistic studies support a redox-neutral radical relay pathway enabled by in situ-generated,catalytic TDRAs.
基金the National Key R&D Program of China(No.2021YFF1200203 to G.W.and 2018YFA0903500 to F.Z.)Hubei Provincial Key R&D program(2021BAA168 to Y.W.)+2 种基金Shen-Zhen Science and Technology Program(JCYJ20220530160805011 to F.Z.)the interdisciplinary research program of Huazhong University of Science and Technology(HUST)(2023JCYJ001 to F.Z.)the China Postdoctoral Science Foundation(2023M741259 to X.Y.)for financial supports.
文摘Comprehensive Summary The implementation of divergent protein engineering on the natural transaminase Vf-ω-TA led to the development of two effective mutants(M2 and M8),enabling the enzymatic synthesis of chiral amine precursors of Rivastigmine and Apremilast,respectively.The evolution of the enzymes was guided by crystal structures and a focused mutagenesis strategy,allowing them to effectively address the challenging ketone substrates with significant steric hindrance.Under the optimized reaction parameters,transamination proceeded smoothly in good conversions and with perfect stereochemical control(>99%ee).These processes utilize inexpensiveα-methylbenzylamine as an amine donor and avoid the continuous acetone removal and costly LDH/GDH/NADH systems.
基金support from the National Natural Science Foundation of China(Grant Nos.22371219,22193011,21971120,21933008 and 22101191)National Science&Technology Fundamental Resource Investigation Program of China(No.2018FY201200)the Fundamental Research Funds for the Central Universities.W.Z.is grateful for the financial support from the program of China Scholarship Council(No.202206240054).
文摘Comprehensive Summary Phthalides serve as core structures pervasive in a wide array of natural products and drug molecules,which display a diverse array of biological activities.We report herein a highly efficient dynamic kinetic resolution of 3-hydroxyphthalides by chiral isothioureas(ITUs)catalyzed asymmetric acylation,facilitating the effective synthesis of a variety of chiral phthalidyl esters with good yields and enantioselectivities.Notably,this reaction features mild reaction conditions,expansive substrate scope as well as good functional group compatibility.In addition,the practicality of this method is underscored by the large-scale synthesis,reduced catalyst loading experiment and the synthesis of the chiral phthalidyl ester prodrug.
