Electrocatalytic organic synthesis has attracted considerable research attention because it is an efficient and eco-friendly strategy for converting energy sources to value-added chemicals.Defect engineering is a prom...Electrocatalytic organic synthesis has attracted considerable research attention because it is an efficient and eco-friendly strategy for converting energy sources to value-added chemicals.Defect engineering is a promising strategy for regulating the electronic structure and charge density of electrocatalysts.It endows electrocatalysts with excellent physical and physicochemical properties and optimizes the adsorption energy of the reaction intermediates to reduce the kinetic barriers of the electrosynthesis reaction.Herein,the recent advances related to the use of electrocatalysts for organic synthesis with respect to defects are systematically reviewed.The roles of defects in anodic and cathodic reactions,such as the syntheses of alkanes,alkenes,alcohols,aldehydes,amides,and carboxylic acids,are reviewed.Furthermore,the relationship between the defective structure and electrocatalytic activity is discussed by combining experimental results and theoretical calculations.Finally,the challenges,opportunities,and development prospects of defective electrocatalysts are examined to promote the development of the field of electrocatalytic organic synthesis.This review is expected to help understand the vital role of defects in catalytic processes and the controllable synthesis of efficient electrocatalysts for the production of high-value chemicals.展开更多
Porous carbon materials have attracted much attention in the field of organic synthesis in recent years,due to their tunable properties,excellent catalytic activity and stability.Biomass-based carbohydrates emerge as ...Porous carbon materials have attracted much attention in the field of organic synthesis in recent years,due to their tunable properties,excellent catalytic activity and stability.Biomass-based carbohydrates emerge as an ideal precursor for the generation of these materials owing to their renewability,low cost,non-toxicity and high content of functional groups.Thus,carbon materials prepared from carbohydrates is of considerable importance for the sustainable development of organic chemistry.The present review not only summarizes recent examples of carbohydrate-derived porous carbon material-catalyzed organic reactions including the oxidation,hydrogenation,cross-coupling,esterification and condensation reactions,but also introduces the preparation and functionalization strategies of these materials.Furthermore,the challenges and opportunities of organic synthesis over these sustainable materials have also been addressed.This review will stimulate further research on exploring novel carbohydrate-derived porous carbon materials and new sustainable organic synthetic processes over these materials.展开更多
There is an increasing demand of using the low-cost and sustainable cobalt to replace its noble congeners(rhodium and iridium)as reflected by the recent upsurge of cobalt catalysis in the diverse organic transformatio...There is an increasing demand of using the low-cost and sustainable cobalt to replace its noble congeners(rhodium and iridium)as reflected by the recent upsurge of cobalt catalysis in the diverse organic transformations.Since all the redox reactivity of cobalt catalysis highly relies on the capability of the interconversion between their oxidation states(most frequently+1,+2 and+3),electrochemistry perfectly meets such a require ment owing to its outstanding perfo rmance in the redox manipulation.In this review,we highlight the recent advances in the merger of cobalt catalysis and electrochemistry in organic synthesis.展开更多
Organic synthesis driven by heterogeneous catalysis is a central research theme to both fundamental research and industrial production of fine chemicals.However,the employment of stoichiometric strong oxidizing or red...Organic synthesis driven by heterogeneous catalysis is a central research theme to both fundamental research and industrial production of fine chemicals.However,the employment of stoichiometric strong oxidizing or reducing reagents(e.g.,K_(2)Cr_(2)O_(7) and LiAlH_(4))and harsh reaction conditions(e.g.,high temperature and pressure)always leads to the products of overreaction and other by-product residues(e.g.,salt and acid waste).Thus the poor control of product selectivity and tremendous energy consumption result in the urgent demand to develop novel technologies for heterogeneous catalysis.Given the current global theme of development in CO_(2) reduction and sustainable energy utilization,one promising protocol is heterogeneous photocatalysis.It enables sustainable solar-to-chemical energy conversion under mild conditions(e.g.,room temperature,ambient pressure,and air as the oxidant)and offers unique reaction pathways for improved selectivity control.To accurately tailor the selectivity of desired products,the electronic structure(e.g.,positions of valence-band maximum and conduction-band minimum),geometric structure(e.g.,nanorod,nanosheet,and porous morphology),and surface chemical micro-environment(e.g.,vacancy sites and co-catalysts)of heterogeneous photocatalysts require rational design and construction.In this review,we will briefly analyze some effective photocatalytic systems with the excellent regulation ability of product selectivity in organic transformations(mainly oxidation and reduction types)under visible light irradiation,and put forward opinions on the optimal fabrication of nanostructured photocatalysts to realize selective organic synthesis.展开更多
The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR ...The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.展开更多
To study the dynamic behavior of a process,time-resolved data are collected at different time instants during each of a series of experiments,which are usually designed with the design of experiments or the design of ...To study the dynamic behavior of a process,time-resolved data are collected at different time instants during each of a series of experiments,which are usually designed with the design of experiments or the design of dynamic experiments methodologies.For utilizing such time-resolved data to model the dynamic behavior,dynamic response surface methodology(DRSM),a datadriven modeling method,has been proposed.Two approaches can be adopted in the estimation of the model parameters:stepwise regression,used in several of previous publications,and Lasso regression,which is newly incorporated in this paper for the estimation of DRSM models.Here,we show that both approaches yield similarly accurate models,while the computational time of Lasso is on average two magnitude smaller.Two case studies are performed to show the advantages of the proposed method.In the first case study,where the concentrations of different species are modeled directly,DRSM method provides more accurate models compared to the models in the literature.The second case study,where the reaction extents are modeled instead of the species concentrations,illustrates the versatility of the DRSM methodology.Therefore,DRSM with Lasso regression can provide faster and more accurate datadriven models for a variety of organic synthesis datasets.展开更多
Recently,a bifunctional CdS/MoO_(2)/MoS_(2) photocatalyst has been reported for coupling hydrogen production and pyruvic acid synthesis.MoS_(2) and MoO_(2),which are synthesized in one step,facilitate the bifunctional...Recently,a bifunctional CdS/MoO_(2)/MoS_(2) photocatalyst has been reported for coupling hydrogen production and pyruvic acid synthesis.MoS_(2) and MoO_(2),which are synthesized in one step,facilitate the bifunctional integration of photocatalytic hydrogen evolution and pyruvic acid synthesis by accepting photogen-erated electrons and holes,respectively.This work inspires the new idea of coupling hydrogen production with selective organic synthesis to obtain green hydrogen and high-value products.展开更多
Recently,piezocatalysis has attracted considerable attention as a new type of renewable mechanical energy conversion technology,which relies on the strain induced polarization of the piezoelectric material.This new te...Recently,piezocatalysis has attracted considerable attention as a new type of renewable mechanical energy conversion technology,which relies on the strain induced polarization of the piezoelectric material.This new technology has been extensively applied in the applications of water splitting,water remediation,gas purification and tumor therapy.Despite the rapid development in the piezo-catalysis,the utilization of piezoelectric materials for synthetic purpose is still under exploration.Piezoelectric means to promote or-ganic reactions expand the scope of piezoelectrically mediated reactions and show successes in both organic and polymer synthesis.Herein,we provide a comprehensive review on recent progress of piezoelectrically mediated reactions,catalytic mechanisms and applications in the last few years.The limitations and future directions of this area are also discussed.We believe this review will provide new insights into the underlying mechanism of piezoelectric mediated electron transfer process and guide the design of new chemistry.展开更多
Metal-organic frameworks(MOFs)are emerging as one of the most intriguing classes of heterogeneous photocatalysts owing to their abundant structures,tunable porosity,and versatile functions.The advantages of bottom-up ...Metal-organic frameworks(MOFs)are emerging as one of the most intriguing classes of heterogeneous photocatalysts owing to their abundant structures,tunable porosity,and versatile functions.The advantages of bottom-up design and reticular synthesis render MOF materials with desired photocatalytic properties for targeted reactions.In this review,we discussed the design and synthesis of MOF-based photocatalysts as well as strategies for enhancing photocatalytic performance.Recent progress on MOFs as platforms for photocatalytic aerobic oxidation reactions was summarized and categorized according to the types of bond formation.We hope this review will give an in-depth insight into MOF-based photocatalytic systems for not only aerobic oxidation reactions but also other organic transformations.A brief outlook on the challenges and opportunities of MOFs as heterogeneous photocatalysts is provided at the end of the review.展开更多
Metal-free heterogeneous photocatalysts provide an environmental-friendly and cost-efficient avenue for green organic synthesis.Covalent organic frameworks(COFs)as heterogeneous photocatalysts showcase promising poten...Metal-free heterogeneous photocatalysts provide an environmental-friendly and cost-efficient avenue for green organic synthesis.Covalent organic frameworks(COFs)as heterogeneous photocatalysts showcase promising potential in the field of photocatalytic organic reactions due to their high porosity,insolubility and tailor-made functions.However,thus far,COF-based catalysts only mediated a few types of reactions.Herein,we developed a series of isoreticular nitrogen-rich covalent organic frameworks(N-COFs)with comparable porous structures as photocatalysts which effectively mediated the borylation of aryl iodides with broad substrate scope.Remarkably,6N-COF exhibits excellent photocatalytic efficiency and superior recyclability.It suggests a new pathway to construct efficient heterogeneous photocatalysts for the borylation of aryl halides.展开更多
Catalysts can accelerate the chemical reaction rate and effectively promote the molecules transformation,which is of great significance in the research of chemical industry and material science.The extreme utilization...Catalysts can accelerate the chemical reaction rate and effectively promote the molecules transformation,which is of great significance in the research of chemical industry and material science.The extreme utilization of reactive sites has led to the emergence and development of atomically dispersed materials(ADMs).The highly active coordination unsaturated metal sites and fully utilized metal atoms make ADMs show great potential in catalytic reactions.The adjustment of coordination environment and electronic structure provides more possibilities for constructing reactive centers with different properties.This review summarized the application and research progress of ADMs in different fields.The design strategy and structure–activity relationship of ADMs for specific reactions were summarized and analyzed.Moreover,we also provided advices for the challenges and opportunities faced by ADMs in catalytic reactions.展开更多
Noble-metal-free photocatalysts with high and stable performance provide an environmentally-friendly and cost-efficient route for green organic synthesis.In this work,CdS nanoparticles with small particle size and dif...Noble-metal-free photocatalysts with high and stable performance provide an environmentally-friendly and cost-efficient route for green organic synthesis.In this work,CdS nanoparticles with small particle size and different amount were successfully deposited on the surface of covalent organic frameworks(COFs).The deposition of suitable content of CdS on COFs could not only modify the light adsorption ability and the intrinsic electronic properties,but also enhance the photocatalytic activity and cycling performance of CdS for the selective oxidation of aromatic alcohols under visible light.Especially,COF/CdS-3 exhibited the highest yield(97.1%)of benzalde hyde which is approximately 2.5 and 15.9 times as that of parental CdS and COF,respectively.The results show that the combination of CdS and COF can improve the utilization of visible light and the separation of photo-generated charge carriers,and COF with theπ-conjugated system as supports for CdS nanoparticles could provide efficient electron transport channels and improve the photocatalytic performance.Therefore,this kind of COF-supported photocatalysts with accelerated photo-induced electrons and charge-carrier separation between semiconductors possesses great potentials in future green organic synthesis.展开更多
The rational fabrication of photocatalysts with dual functions upon visible light, such as photocatalytic radioactive U(Ⅵ)reduction and value-added organic oxidation, is highly desirable but remains huge challenge. H...The rational fabrication of photocatalysts with dual functions upon visible light, such as photocatalytic radioactive U(Ⅵ)reduction and value-added organic oxidation, is highly desirable but remains huge challenge. Here, we couple the photocatalytic U(Ⅵ) reduction with the oxidative organic synthesis to one system using novel extended π-conjugated framework(Cu@ThTCPP) without the expense of sacrificial reagents. Noticeably, the as-prepared Cu@Th-TCPP linked by tetratopic tetrakis(4-carboxyphenyl)porphyrin(TCPP) ligand and unique Th(μ-O)(HCOO)(HO)secondary building unit(SBU) exhibits significantly enhanced activity when the photocatalytic U(Ⅵ) reduction and thioanisole oxidation were integrated to one system.Further experimental characterizations demonstrate that the highly conjugated framework of Cu@Th-TCPP is good for the charge transfer and separation, while incorporating Cusite further accelerates the charge-carrier dynamics, thus giving rise to the dual-functional property. Apparently, this strategy conforms to atomic economy, opens a new horizon to address radioactive environmental pollution in natural water systems and soils, and simultaneously produces valuable chemicals.展开更多
The metal-free S–S bond exchange reaction of symmetrical disulfides catalyzed by NFSI is described. This novel protocol provides a facile and efficient approach to accessing important unsymmetrical disulfides.Further...The metal-free S–S bond exchange reaction of symmetrical disulfides catalyzed by NFSI is described. This novel protocol provides a facile and efficient approach to accessing important unsymmetrical disulfides.Furthermore, this strategy could also be utilized in the late-stage functionalization of amino acids, drugs,and natural products. The broad substrate scope, good functional group tolerance and easy accessibility of catalyst indicate that this strategy affords a green and practical complementary method to various unsymmetrical disulfides.展开更多
Traditional synthesis made outstanding achievements but still suffers various drawbacks,such as manual operation,poor efficiency,and lack of reproducibility.Thanks to the development of laboratory automation,synthetic...Traditional synthesis made outstanding achievements but still suffers various drawbacks,such as manual operation,poor efficiency,and lack of reproducibility.Thanks to the development of laboratory automation,synthetic chemistry is now chasing a pavement from a labor-intensive process to intelligent automation.Herein,we highlight some of the most recent representative breakthroughs in automated synthesis and present an outlook for this field.We hope this Topic can arouse chemists'interest in automated synthe-sis and drive synthetic automation to a better intelligent and automatic way.展开更多
A simple electrochemically mediated method for the conversion of nitroarenes to aryl boronic esters is presented.Electrochemical borylation of a diverse range of nitroarenes,including the late-stage borylation of bioa...A simple electrochemically mediated method for the conversion of nitroarenes to aryl boronic esters is presented.Electrochemical borylation of a diverse range of nitroarenes,including the late-stage borylation of bioactive molecules,is furnished at room temperature under simple conditions,thereby demonstrating the broad utility and functional-group tolerance of this protocol.This transformation provides a convenient and practical access to aryl boronic esters from widely available nitroarenes,which would significantly streamline the synthetic process of diverse functionalized arenes.展开更多
Dihydropyran(DHP)compounds are not only found in natural products and bioactive molecules,but also serve as important precursors in organic synthesis.Nonetheless,traditional methods for the construction of such compou...Dihydropyran(DHP)compounds are not only found in natural products and bioactive molecules,but also serve as important precursors in organic synthesis.Nonetheless,traditional methods for the construction of such compounds are usually limited to disubstituted DHPs.To address this synthetic challenge,reported here is an efficient electrochemical strategy toward the selenated and trifluoromethylated DHP compounds.The reaction proceeded smoothly under mild electrolysis conditions.The broad substrate scope(>50 examples)and scalable synthesis demonstrated the complexity-building potential of the strategy.Initial mechanistic studies reveal that cyclization may involve a radical process.This protocol may promote the further development of diversified synthesis of multi-substituted dihydropyran.展开更多
Carbon nanotubes(CNTs)are an emerging nanomaterial because of their outstanding performance in various applications.In recent years,the segment molecules of CNTs,referred to as carbon nanorings(CNRs)or carbon nanobelt...Carbon nanotubes(CNTs)are an emerging nanomaterial because of their outstanding performance in various applications.In recent years,the segment molecules of CNTs,referred to as carbon nanorings(CNRs)or carbon nanobelts(CNBs),have gained attention for their unique structures and properties,as well as their potential as seed molecules for the precise synthesis of CNTs.CNBs are rigid and thick segments of CNTs whose synthesis has been addressed by scientists fascinated by the uniqueness of CNBs long before the discovery of CNTs.After 60 years of efforts by synthetic chemists all over the world,the synthesis of the first CNB,(6,6)CNB,was achieved by our group in 2017.Since this milestone,diverse types of nanobelts have been synthesized through various synthetic routes,thereby demonstrating their photophysical,magnetic,and redox properties derived from rigid belt structures.The applications of CNBs have also been introduced recently.The formation of the host−guest complex,transformation to three-dimensional molecules,and measurement of conductivity have been reported for CNBs.This paper summarizes the brief history and perspective of CNBs.Further synthetic campaigns and aggressive application of CNBs would create novel and groundbreaking scenes in materials science.展开更多
Transition-metal-catalyzed C–H bond functionalization has attracted tremendous attention as an increasingly important protocol for the construction of C–C and C–X bonds.In particular,C–H bond functionalization ass...Transition-metal-catalyzed C–H bond functionalization has attracted tremendous attention as an increasingly important protocol for the construction of C–C and C–X bonds.In particular,C–H bond functionalization assisted by the phosphorus-containing directing groups has made significant progress in the past few years.A series of valuable phosphorous compounds,especially phosphine ligands have been provided conveniently.This review comprehensively describes recent advances in transition-metal-catalyzed C–H bond functionalization assisted by the phosphorus-containing directing groups,highlights its potential applications in organic synthesis,and gives some insights into future advances.展开更多
Electrocatalytic hydrogenation(ECH)of organics using water as hydrogen donors has been regarded as a green organic reduction technique to replace traditional chemical reactions that use sacrificial chemicals.The devel...Electrocatalytic hydrogenation(ECH)of organics using water as hydrogen donors has been regarded as a green organic reduction technique to replace traditional chemical reactions that use sacrificial chemicals.The development of ECH process provides potential applications in the production of value-added chemicals owing to its low energy consumption,low pollution,high safety,and superior sustainability.However,its application is limited by the low conversion rate and poor selectivity toward desired products.The efficiency of ECH can be improved by rational design of electrocatalysts.This review covers several representative electrocatalytic systems(aldehydes,ketones,phenolic organics,alkynes,and organonitrogen compounds)and summarizes different ECH mechanisms,followed by thorough discussion on the modification strategies of electrocatalysts that are currently adopted to enhance the catalytic performance.Finally,in view of the current challenges for ECH,we discuss possible future directions in the field,aiming to provide guidance to the catalyst design toward highly efficient ECH reactions over different organic feedstocks.展开更多
基金supported by the National Key Research and Development Program of China(No.2020YFA0710000)the National Natural Science Foundation of China(Nos.22122901 and 21902047)+1 种基金the Provincial Natural Science Foundation of Hunan(Nos.2020JJ5045,2021JJ20024,and 2021RC3054)the Shenzhen Science and Technology Program(No.JCYJ20210324140610028).
文摘Electrocatalytic organic synthesis has attracted considerable research attention because it is an efficient and eco-friendly strategy for converting energy sources to value-added chemicals.Defect engineering is a promising strategy for regulating the electronic structure and charge density of electrocatalysts.It endows electrocatalysts with excellent physical and physicochemical properties and optimizes the adsorption energy of the reaction intermediates to reduce the kinetic barriers of the electrosynthesis reaction.Herein,the recent advances related to the use of electrocatalysts for organic synthesis with respect to defects are systematically reviewed.The roles of defects in anodic and cathodic reactions,such as the syntheses of alkanes,alkenes,alcohols,aldehydes,amides,and carboxylic acids,are reviewed.Furthermore,the relationship between the defective structure and electrocatalytic activity is discussed by combining experimental results and theoretical calculations.Finally,the challenges,opportunities,and development prospects of defective electrocatalysts are examined to promote the development of the field of electrocatalytic organic synthesis.This review is expected to help understand the vital role of defects in catalytic processes and the controllable synthesis of efficient electrocatalysts for the production of high-value chemicals.
基金supported by the National Key Research and Development Project(No.2021YFC2100100)National Natural Science Foundation of China(Nos.32001266,22007049)Natural Science Foundation of Jiangsu Province(No.BK20200728)。
文摘Porous carbon materials have attracted much attention in the field of organic synthesis in recent years,due to their tunable properties,excellent catalytic activity and stability.Biomass-based carbohydrates emerge as an ideal precursor for the generation of these materials owing to their renewability,low cost,non-toxicity and high content of functional groups.Thus,carbon materials prepared from carbohydrates is of considerable importance for the sustainable development of organic chemistry.The present review not only summarizes recent examples of carbohydrate-derived porous carbon material-catalyzed organic reactions including the oxidation,hydrogenation,cross-coupling,esterification and condensation reactions,but also introduces the preparation and functionalization strategies of these materials.Furthermore,the challenges and opportunities of organic synthesis over these sustainable materials have also been addressed.This review will stimulate further research on exploring novel carbohydrate-derived porous carbon materials and new sustainable organic synthetic processes over these materials.
基金Financial support from the National Natural Science Foundation of China(No.21901041)Fuzhou University(No.510841)is gratefully acknowledged。
文摘There is an increasing demand of using the low-cost and sustainable cobalt to replace its noble congeners(rhodium and iridium)as reflected by the recent upsurge of cobalt catalysis in the diverse organic transformations.Since all the redox reactivity of cobalt catalysis highly relies on the capability of the interconversion between their oxidation states(most frequently+1,+2 and+3),electrochemistry perfectly meets such a require ment owing to its outstanding perfo rmance in the redox manipulation.In this review,we highlight the recent advances in the merger of cobalt catalysis and electrochemistry in organic synthesis.
基金This work was supported by the National Key R&D Program of China(No.2020YFA0406103)the National Natural Science Foundation of China(NSFC)(Nos.21725102 and 91961106)+1 种基金the Dalian National Laboratory for Clean Energy(DNL)Cooperation Fund,Chinese Academy of Sciences(CAS)(No.DNL201922)the startup grant from University of Science and Technology of China(USTC)(No.KY2260080010).
文摘Organic synthesis driven by heterogeneous catalysis is a central research theme to both fundamental research and industrial production of fine chemicals.However,the employment of stoichiometric strong oxidizing or reducing reagents(e.g.,K_(2)Cr_(2)O_(7) and LiAlH_(4))and harsh reaction conditions(e.g.,high temperature and pressure)always leads to the products of overreaction and other by-product residues(e.g.,salt and acid waste).Thus the poor control of product selectivity and tremendous energy consumption result in the urgent demand to develop novel technologies for heterogeneous catalysis.Given the current global theme of development in CO_(2) reduction and sustainable energy utilization,one promising protocol is heterogeneous photocatalysis.It enables sustainable solar-to-chemical energy conversion under mild conditions(e.g.,room temperature,ambient pressure,and air as the oxidant)and offers unique reaction pathways for improved selectivity control.To accurately tailor the selectivity of desired products,the electronic structure(e.g.,positions of valence-band maximum and conduction-band minimum),geometric structure(e.g.,nanorod,nanosheet,and porous morphology),and surface chemical micro-environment(e.g.,vacancy sites and co-catalysts)of heterogeneous photocatalysts require rational design and construction.In this review,we will briefly analyze some effective photocatalytic systems with the excellent regulation ability of product selectivity in organic transformations(mainly oxidation and reduction types)under visible light irradiation,and put forward opinions on the optimal fabrication of nanostructured photocatalysts to realize selective organic synthesis.
文摘The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.
基金Yachao Dong is grateful for the financial support of Fundamental Research Funds for the Central Universities(Grant No.DUT20RC(3)070).
文摘To study the dynamic behavior of a process,time-resolved data are collected at different time instants during each of a series of experiments,which are usually designed with the design of experiments or the design of dynamic experiments methodologies.For utilizing such time-resolved data to model the dynamic behavior,dynamic response surface methodology(DRSM),a datadriven modeling method,has been proposed.Two approaches can be adopted in the estimation of the model parameters:stepwise regression,used in several of previous publications,and Lasso regression,which is newly incorporated in this paper for the estimation of DRSM models.Here,we show that both approaches yield similarly accurate models,while the computational time of Lasso is on average two magnitude smaller.Two case studies are performed to show the advantages of the proposed method.In the first case study,where the concentrations of different species are modeled directly,DRSM method provides more accurate models compared to the models in the literature.The second case study,where the reaction extents are modeled instead of the species concentrations,illustrates the versatility of the DRSM methodology.Therefore,DRSM with Lasso regression can provide faster and more accurate datadriven models for a variety of organic synthesis datasets.
基金financially supported by the International Postdoctoral Exchange Fellowship Program(No.PC2022051)the China Postdoctoral Science Foundation(Nos.2021TQ0311 and 2021M702990).
文摘Recently,a bifunctional CdS/MoO_(2)/MoS_(2) photocatalyst has been reported for coupling hydrogen production and pyruvic acid synthesis.MoS_(2) and MoO_(2),which are synthesized in one step,facilitate the bifunctional integration of photocatalytic hydrogen evolution and pyruvic acid synthesis by accepting photogen-erated electrons and holes,respectively.This work inspires the new idea of coupling hydrogen production with selective organic synthesis to obtain green hydrogen and high-value products.
基金supported by the National Natural Science Foundation of China(22101195 and 21925107)the Natural Science Foundation of liangsu Province(BK20210732)+2 种基金the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the Program of Innovative Research Team of Soochow UniversityWe thank Dr.Bo Tang for the helpful discussion and support from the Special Key Project of Technology Innovation and Application Development of Chongqing(No.cstc2020jscx-dxwtBx0025).
文摘Recently,piezocatalysis has attracted considerable attention as a new type of renewable mechanical energy conversion technology,which relies on the strain induced polarization of the piezoelectric material.This new technology has been extensively applied in the applications of water splitting,water remediation,gas purification and tumor therapy.Despite the rapid development in the piezo-catalysis,the utilization of piezoelectric materials for synthetic purpose is still under exploration.Piezoelectric means to promote or-ganic reactions expand the scope of piezoelectrically mediated reactions and show successes in both organic and polymer synthesis.Herein,we provide a comprehensive review on recent progress of piezoelectrically mediated reactions,catalytic mechanisms and applications in the last few years.The limitations and future directions of this area are also discussed.We believe this review will provide new insights into the underlying mechanism of piezoelectric mediated electron transfer process and guide the design of new chemistry.
基金supported by the National Natural Science Foundation of China(21731002,21975104,22101099,22150004,22271120)Guangdong Major Project of Basic and Applied Research(2019B030302009)the Outstanding Innovative Talents Cultivation Funded Programs for Doctoral Students of Jinan University(2022CXB007)。
文摘Metal-organic frameworks(MOFs)are emerging as one of the most intriguing classes of heterogeneous photocatalysts owing to their abundant structures,tunable porosity,and versatile functions.The advantages of bottom-up design and reticular synthesis render MOF materials with desired photocatalytic properties for targeted reactions.In this review,we discussed the design and synthesis of MOF-based photocatalysts as well as strategies for enhancing photocatalytic performance.Recent progress on MOFs as platforms for photocatalytic aerobic oxidation reactions was summarized and categorized according to the types of bond formation.We hope this review will give an in-depth insight into MOF-based photocatalytic systems for not only aerobic oxidation reactions but also other organic transformations.A brief outlook on the challenges and opportunities of MOFs as heterogeneous photocatalysts is provided at the end of the review.
基金financially supported by National Natural Science Foundation of China(No.51973153)。
文摘Metal-free heterogeneous photocatalysts provide an environmental-friendly and cost-efficient avenue for green organic synthesis.Covalent organic frameworks(COFs)as heterogeneous photocatalysts showcase promising potential in the field of photocatalytic organic reactions due to their high porosity,insolubility and tailor-made functions.However,thus far,COF-based catalysts only mediated a few types of reactions.Herein,we developed a series of isoreticular nitrogen-rich covalent organic frameworks(N-COFs)with comparable porous structures as photocatalysts which effectively mediated the borylation of aryl iodides with broad substrate scope.Remarkably,6N-COF exhibits excellent photocatalytic efficiency and superior recyclability.It suggests a new pathway to construct efficient heterogeneous photocatalysts for the borylation of aryl halides.
基金supported by the National Key R&D Program of China(No.2018YFA0702003)the National Natural Science Foundation of China(Nos.21890383 and 21871159)+1 种基金the Science and Technology Key Project of Guangdong Province of China(No.2020B010188002)the China Postdoctoral Science Foundation(No.2022M721796).
文摘Catalysts can accelerate the chemical reaction rate and effectively promote the molecules transformation,which is of great significance in the research of chemical industry and material science.The extreme utilization of reactive sites has led to the emergence and development of atomically dispersed materials(ADMs).The highly active coordination unsaturated metal sites and fully utilized metal atoms make ADMs show great potential in catalytic reactions.The adjustment of coordination environment and electronic structure provides more possibilities for constructing reactive centers with different properties.This review summarized the application and research progress of ADMs in different fields.The design strategy and structure–activity relationship of ADMs for specific reactions were summarized and analyzed.Moreover,we also provided advices for the challenges and opportunities faced by ADMs in catalytic reactions.
基金supported by the National Natural Science Foundation of China(No.51802015)National Key Research and Development Program of China(No.2018YFB0605900)+1 种基金Fundamental Research Funds for the Central Universities(No.FRF-TP-20-005A3)Interdisciplinary Research Project for Young Teachers of USTB(Fundamental Research Funds for the Central Universities)(No.FRF-IDRY-19-020)。
文摘Noble-metal-free photocatalysts with high and stable performance provide an environmentally-friendly and cost-efficient route for green organic synthesis.In this work,CdS nanoparticles with small particle size and different amount were successfully deposited on the surface of covalent organic frameworks(COFs).The deposition of suitable content of CdS on COFs could not only modify the light adsorption ability and the intrinsic electronic properties,but also enhance the photocatalytic activity and cycling performance of CdS for the selective oxidation of aromatic alcohols under visible light.Especially,COF/CdS-3 exhibited the highest yield(97.1%)of benzalde hyde which is approximately 2.5 and 15.9 times as that of parental CdS and COF,respectively.The results show that the combination of CdS and COF can improve the utilization of visible light and the separation of photo-generated charge carriers,and COF with theπ-conjugated system as supports for CdS nanoparticles could provide efficient electron transport channels and improve the photocatalytic performance.Therefore,this kind of COF-supported photocatalysts with accelerated photo-induced electrons and charge-carrier separation between semiconductors possesses great potentials in future green organic synthesis.
基金supported by Jiangxi Province Key Laboratory of Synthetic Chemistry(JXSC202004)the Foundation of Jiangxi Educational Committee(GJJ200731)the Natural Science Foundation of Jiangxi Province of China(20192BAB213001)。
文摘The rational fabrication of photocatalysts with dual functions upon visible light, such as photocatalytic radioactive U(Ⅵ)reduction and value-added organic oxidation, is highly desirable but remains huge challenge. Here, we couple the photocatalytic U(Ⅵ) reduction with the oxidative organic synthesis to one system using novel extended π-conjugated framework(Cu@ThTCPP) without the expense of sacrificial reagents. Noticeably, the as-prepared Cu@Th-TCPP linked by tetratopic tetrakis(4-carboxyphenyl)porphyrin(TCPP) ligand and unique Th(μ-O)(HCOO)(HO)secondary building unit(SBU) exhibits significantly enhanced activity when the photocatalytic U(Ⅵ) reduction and thioanisole oxidation were integrated to one system.Further experimental characterizations demonstrate that the highly conjugated framework of Cu@Th-TCPP is good for the charge transfer and separation, while incorporating Cusite further accelerates the charge-carrier dynamics, thus giving rise to the dual-functional property. Apparently, this strategy conforms to atomic economy, opens a new horizon to address radioactive environmental pollution in natural water systems and soils, and simultaneously produces valuable chemicals.
基金the financial support from the National Natural Science Foundation of China (Nos. 21572026, 21702019)Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. SJCX20_0952)Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou University
文摘The metal-free S–S bond exchange reaction of symmetrical disulfides catalyzed by NFSI is described. This novel protocol provides a facile and efficient approach to accessing important unsymmetrical disulfides.Furthermore, this strategy could also be utilized in the late-stage functionalization of amino acids, drugs,and natural products. The broad substrate scope, good functional group tolerance and easy accessibility of catalyst indicate that this strategy affords a green and practical complementary method to various unsymmetrical disulfides.
基金support from Guangzhou Laboratory,Bioland Laboratory,and the National Natural Science Foundation of China(22071249).
文摘Traditional synthesis made outstanding achievements but still suffers various drawbacks,such as manual operation,poor efficiency,and lack of reproducibility.Thanks to the development of laboratory automation,synthetic chemistry is now chasing a pavement from a labor-intensive process to intelligent automation.Herein,we highlight some of the most recent representative breakthroughs in automated synthesis and present an outlook for this field.We hope this Topic can arouse chemists'interest in automated synthe-sis and drive synthetic automation to a better intelligent and automatic way.
基金supported by the National Natural Science Foundation of China(21602096)。
文摘A simple electrochemically mediated method for the conversion of nitroarenes to aryl boronic esters is presented.Electrochemical borylation of a diverse range of nitroarenes,including the late-stage borylation of bioactive molecules,is furnished at room temperature under simple conditions,thereby demonstrating the broad utility and functional-group tolerance of this protocol.This transformation provides a convenient and practical access to aryl boronic esters from widely available nitroarenes,which would significantly streamline the synthetic process of diverse functionalized arenes.
基金supported by the National Key R&D Program of China(2022YFA1505100,2021YFA1500100)the National Natural Science Foundation of China(22031008)+1 种基金the Fundamental Research Funds for the Central Universities(2042022rc0030,2042023kf0108,2042023kf1002)the Science Foundation of Wuhan(2020010601012192)。
文摘Dihydropyran(DHP)compounds are not only found in natural products and bioactive molecules,but also serve as important precursors in organic synthesis.Nonetheless,traditional methods for the construction of such compounds are usually limited to disubstituted DHPs.To address this synthetic challenge,reported here is an efficient electrochemical strategy toward the selenated and trifluoromethylated DHP compounds.The reaction proceeded smoothly under mild electrolysis conditions.The broad substrate scope(>50 examples)and scalable synthesis demonstrated the complexity-building potential of the strategy.Initial mechanistic studies reveal that cyclization may involve a radical process.This protocol may promote the further development of diversified synthesis of multi-substituted dihydropyran.
基金the JST-ERATO program(JPMJER1302 to K.I.)a JSPS KAKENHI grant(JP19H05463 to K.I.).
文摘Carbon nanotubes(CNTs)are an emerging nanomaterial because of their outstanding performance in various applications.In recent years,the segment molecules of CNTs,referred to as carbon nanorings(CNRs)or carbon nanobelts(CNBs),have gained attention for their unique structures and properties,as well as their potential as seed molecules for the precise synthesis of CNTs.CNBs are rigid and thick segments of CNTs whose synthesis has been addressed by scientists fascinated by the uniqueness of CNBs long before the discovery of CNTs.After 60 years of efforts by synthetic chemists all over the world,the synthesis of the first CNB,(6,6)CNB,was achieved by our group in 2017.Since this milestone,diverse types of nanobelts have been synthesized through various synthetic routes,thereby demonstrating their photophysical,magnetic,and redox properties derived from rigid belt structures.The applications of CNBs have also been introduced recently.The formation of the host−guest complex,transformation to three-dimensional molecules,and measurement of conductivity have been reported for CNBs.This paper summarizes the brief history and perspective of CNBs.Further synthetic campaigns and aggressive application of CNBs would create novel and groundbreaking scenes in materials science.
基金supported by the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2022R01007)the National Natural Science Foundation of China(Nos.21971062 and 22171082.)the Start-up Research Grant from Zhejiang Normal University.
文摘Transition-metal-catalyzed C–H bond functionalization has attracted tremendous attention as an increasingly important protocol for the construction of C–C and C–X bonds.In particular,C–H bond functionalization assisted by the phosphorus-containing directing groups has made significant progress in the past few years.A series of valuable phosphorous compounds,especially phosphine ligands have been provided conveniently.This review comprehensively describes recent advances in transition-metal-catalyzed C–H bond functionalization assisted by the phosphorus-containing directing groups,highlights its potential applications in organic synthesis,and gives some insights into future advances.
基金supported by the Fundamental Research Funds for the Central Universities in China(No.20720210010)National Natural Science Foundation of China(No.22001081)+2 种基金the Science and Technology Projects of Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM,Grant No.:HRTP-[2022]-7)Xiamen University.Qiu Jiang acknowledges the China Postdoctoral Science Foundation funded project(2022M710601)the University of Electronic Science and Technology of China for startup funding(Y030212059003039).
文摘Electrocatalytic hydrogenation(ECH)of organics using water as hydrogen donors has been regarded as a green organic reduction technique to replace traditional chemical reactions that use sacrificial chemicals.The development of ECH process provides potential applications in the production of value-added chemicals owing to its low energy consumption,low pollution,high safety,and superior sustainability.However,its application is limited by the low conversion rate and poor selectivity toward desired products.The efficiency of ECH can be improved by rational design of electrocatalysts.This review covers several representative electrocatalytic systems(aldehydes,ketones,phenolic organics,alkynes,and organonitrogen compounds)and summarizes different ECH mechanisms,followed by thorough discussion on the modification strategies of electrocatalysts that are currently adopted to enhance the catalytic performance.Finally,in view of the current challenges for ECH,we discuss possible future directions in the field,aiming to provide guidance to the catalyst design toward highly efficient ECH reactions over different organic feedstocks.
