A highly efficient benzylation of arenes and heteroarenes catalyzed by HfCl4/HfO2 has been developed. Broad scope of benzylation reagents have been used in this process with high yields under mild condition. Additiona...A highly efficient benzylation of arenes and heteroarenes catalyzed by HfCl4/HfO2 has been developed. Broad scope of benzylation reagents have been used in this process with high yields under mild condition. Additionally, the HfO2 can be re-used after the reaction. ？2009 Xin Qin Gao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
Selective formation of pharmaceutical intermediates like diphenylmethane, dimethyldiphenylmethane, benzyl toluene and benzoic acid by liquid phase, toluene benzylation with benzyl chloride as a benzylating agent, was ...Selective formation of pharmaceutical intermediates like diphenylmethane, dimethyldiphenylmethane, benzyl toluene and benzoic acid by liquid phase, toluene benzylation with benzyl chloride as a benzylating agent, was systematically studied over plane clay （K-10, montmorillonite）, plane H-Beta, plane MFI structured titanosilicate （TS-1） and heteropoly acids [HPA, namely dodecatungstophosphoric acid [H3PO4.12WOa-xH2O] （TPA）, dodeca-molybdo phosphoric acid ammonium salt hydrate [H12Mo12N3040P＋aq] （DMAA）, sodium tungstate hydrated purified [Na12WO4.2H2O] （STH）] supported on clay, H-beta and TS-1. The 20%TPA/Clay, 30%TPA/H-Beta and 30%TPA/TS-1, were observed to be the best catalyst samples over plane clay, plane H-Beta and plane TS-1. The catalyst samples are compared with respect to benzyl chloride conversion and selectivities for diphenylmethane, dimethyl-diphenylmethane, benzyl toluene and benzoic acid. The reaction follows the pseudo-first order rate power law model. The apparent rate constants are calculated and compared with the reported ones.展开更多
An SN2-based photochemical strategy using dithiocarbamate anion as catalyst was developed for the activation of benzyl halides,which are extremely challenging to be applied as radical precursors in visible light photo...An SN2-based photochemical strategy using dithiocarbamate anion as catalyst was developed for the activation of benzyl halides,which are extremely challenging to be applied as radical precursors in visible light photocatalysis.With this transition-metal-free and oxidant-free protocol,the benzylation(or cyanomethylation)of various heterocycles including quinoxalin-2(1H)-ones,coumarin,2-phenyl-2H-indazole,1-methyl-5-phenylpyrazin-2(1H)-one,1-(fluoromethyl)cinnolin-4(1H)-one,and 2,4-dibenzyl-1,2,4-triazine-3,5(2H,4H)-dione could be realized(46 examples,up to 98%yield).Importantly,some biologically relevant 3-benzylquinoxalin-2(1H)-ones were also be synthesized under mild conditions.展开更多
A new debenzylation of benzyl esters by silica-supported sodium hydrogen sulfate is described. The debenzylation could be achieved selectively and efficiently in good to excellent yields without affecting sensitive fu...A new debenzylation of benzyl esters by silica-supported sodium hydrogen sulfate is described. The debenzylation could be achieved selectively and efficiently in good to excellent yields without affecting sensitive functional groups such as nitro, unsaturated bonds, and ethyl ester.展开更多
The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH3 atmosphere with different time. The resultant zeolites were characterized by a complementary c...The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH3 atmosphere with different time. The resultant zeolites were characterized by a complementary combination of X-ray power diffraction(XRD), scanning electron microscopy(SEM),transmission electron microscopy(TEM), pyridine-IR spectroscopy and N2 adsorption–desorption isotherms. The analyses showed that the nitridation didn’t destroy the crystallinity and specific surface area of zeolites, and the acidity of zeolites can be tailored by tuning the time of nitridation, resulting in the different concentration ratios of Br?nsted-to-Lewis(B/L) acid sites. Moreover, the nitrided zeolites exhibited high selectivity to 2-benzyl-1,3,5-trimethylbenzene than parent silica pillared MFI zeolite nanosheets in benzylation of mesitylene with benzyl alcohol. A balance between Br?nsted acid sites and Lewis acid sites can inhibit the self-etherification of benzyl alcohol and enhance the selectivity of alkylated product. These experimental data implied that nitridation was an effective method to modulate the acidity of zeolites and the synergy between Br?nsted acid sites and Lewis acid sites was a decisive factor to determine the selectivity.展开更多
In the presence of Nafion/SiO2 nanocomposite catalyst, the benzylation of aromatic compounds with benzyl chloride proceeded to afford diphenylmethane derivatives in high yields. The catalyst showed high catalytic ac...In the presence of Nafion/SiO2 nanocomposite catalyst, the benzylation of aromatic compounds with benzyl chloride proceeded to afford diphenylmethane derivatives in high yields. The catalyst showed high catalytic activity not only for electron-rich aromatic compounds, but also for electron-poor aromatic compounds. Under identical conditions, the self-benzylation of benzyl chloride, and dibenzylation and/or multi-benzylation of aromatic compounds were negligible.展开更多
An efficient BF3.OEt2-promoted benzylation of arenes and heteroarenes with various benzyl ether derivatives has been developed. This method provided alternative access to valuable diarylmethane in good yields under mi...An efficient BF3.OEt2-promoted benzylation of arenes and heteroarenes with various benzyl ether derivatives has been developed. This method provided alternative access to valuable diarylmethane in good yields under mild conditions via an easy work-up procedure.展开更多
Herein,we have developed a sustainable linear paired electrolysis strategy for the redox-neutral benzylation of N-heteroarenes with benzyl halides using solid ion resin as the recyclable electrolyte.This method suffic...Herein,we have developed a sustainable linear paired electrolysis strategy for the redox-neutral benzylation of N-heteroarenes with benzyl halides using solid ion resin as the recyclable electrolyte.This method sufficiently utilizes both cathodic and anodic reactions to produce a variety of benzylated Nheteroarenes,features high atom-and step-economy,excellent energy efficiency,operational simplicity,good functional group tolerance,mild conditions and no requirement of sacrifice reagent and base additive.Importantly,the inexpensive and commercially available solid ion resin electrolyte was validated in both gram-scale synthesis and electrolyte cycling experiment.We hope this strategy not only provides a sustainable synthetic strategy for benzylated compounds but also develops the further utilization of ion resin in electrosynthesis as well as linear paired electrolysis.展开更多
The development of sustainable and efficient synthetic methodologies for high-valued chemicals from renewable resources is one of the principal aims of chemical industries.Herein,we document the combination of photoca...The development of sustainable and efficient synthetic methodologies for high-valued chemicals from renewable resources is one of the principal aims of chemical industries.Herein,we document the combination of photocatalytic PCET and SCS-enabled direct C-H benzylation of N-heteroarenes with benzaldehydes as the benzyl sources.Avariety of benzylated N-heteroarenes was obtained in moderate to excellent yields at room temperature under metal-,oxidant-free and mild conditions in continuous-flow mode.Mechanistic studies indicated that this benzylation proceeded via PCET activation of benzaldehydes to yield ketyl radicals,the addition of the ketyl radicals to N-heteroarenes to form C-C(OH)bonds,the SCS cleavage to produce benzylic radical and HAT process to deliver the benzylated products.展开更多
Transition-metal mediated activation of inert chemical bonds is an ongoing topic in homogeneous catalysis.In view of the abundance and accessibility of alkylarenes and benzylamines,the use of them as benzyl source in ...Transition-metal mediated activation of inert chemical bonds is an ongoing topic in homogeneous catalysis.In view of the abundance and accessibility of alkylarenes and benzylamines,the use of them as benzyl source in catalytic benzylation reactions via benzylic C-H and C-N bond activation is highly desirable.Indeed,compared with the traditional approaches with benzyl halide as the substrates,benzylation reactions via C-H and C-N bond cleavage provide more efficient,atom-economic strategies to access myriads of synthetically important molecules.In this account,our group's efforts on catalytic benzylation reactions via directed C-H activation,nondirected C-H activation and C-N bond activation are summarized.展开更多
The benzylation and allylation of 4-nitrobenzaldehyde (1) could be controlled chemoselectively by using different phase transfer catalyst (FTC) and different metal catalysts. And then, benzylation and allylation of 1 ...The benzylation and allylation of 4-nitrobenzaldehyde (1) could be controlled chemoselectively by using different phase transfer catalyst (FTC) and different metal catalysts. And then, benzylation and allylation of 1 with various organic halides has been realized in high yields in aqueous media.展开更多
Polysaceharide is a polyhydroxyl maeromolecular compound. Owing to the influence of the intermolecular and intramolecular hydrogenbonds and difficulty in achieving reaction in solution, it is difficult to obtain produ...Polysaceharide is a polyhydroxyl maeromolecular compound. Owing to the influence of the intermolecular and intramolecular hydrogenbonds and difficulty in achieving reaction in solution, it is difficult to obtain products of its complete or selective substitution in the research of polysaccharide modification or structure. The展开更多
α-Aryl-α,α-difluoroacetophenones(DFAPs)are developed as a new class of difluorobenzylation reagents that can be facilely prepared from readily available and cheap starting materials.In situ carbon-carbon bond cleav...α-Aryl-α,α-difluoroacetophenones(DFAPs)are developed as a new class of difluorobenzylation reagents that can be facilely prepared from readily available and cheap starting materials.In situ carbon-carbon bond cleavage of electron-deficient DFAPs gives difluorobenzyl carbanions that undergo base-catalyzed nucleophilic addition to isatins.展开更多
Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely bee...Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition.In this study,a series of bimetallic nickel-iron phosphide(Ni_(x)Fe_(2-x)P,where 0<x<2)cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus(RP)for the photocatalytic selective oxidation of benzyl alcohol(BA)coupled with hydrogen production.The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H_(2)yield.The RP regulated by bimetallic phosphide cocatalysts(Ni_(x)Fe_(2-x)P)demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts(Ni_(2)P and Fe2P).In particular,the RP regulated by Ni_(1.25)Fe_(0.75)P exhibited the best photocatalytic performance.In addition,experimental and theoretical calculations further illustrated that Ni_(1.25)Fe_(0.75)P,with the optimized electronic structure,possessed good electrical conductivity and provided strong adsorption and abundant active sites,thereby accelerating electron migration and lowering the reaction energy barrier of RP.This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.展开更多
A general metal-free photochemcial oxidation of benzylic C—H bonds has been successfully accomplished via a hydrogen atom transfer(HAT)process.A range of high value-added aromatic ketones were facilely synthesized wi...A general metal-free photochemcial oxidation of benzylic C—H bonds has been successfully accomplished via a hydrogen atom transfer(HAT)process.A range of high value-added aromatic ketones were facilely synthesized with high chemoselectivity under mild conditions.Moreover,the mild conditions by using air as the oxidant render the developed proto-col more ecofriendly and environmentally sustainable.展开更多
Ni_(2)CoS_(4)was prepared by the liquid‑phase method and applied to the benzyl alcohol electro‑oxidation reaction(BAOR),demonstrating excellent catalytic activity[with a current density of 271 mA·cm^(-2)at 1.40 V...Ni_(2)CoS_(4)was prepared by the liquid‑phase method and applied to the benzyl alcohol electro‑oxidation reaction(BAOR),demonstrating excellent catalytic activity[with a current density of 271 mA·cm^(-2)at 1.40 V(vs RHE)]and long‑term stability.The S‑anion effect can regulate the charge distribution on the catalyst surface,thereby enhancing the additional adsorption capacity of OH-at the Co sites.By combining material characterization and theoretical calculations,it can be observed that this process can increase the concentration of the OH^(*)intermediate,accelerate the activation process of the Ni site,and ultimately achieve an improvement in overall activity and stability.展开更多
The direct deoxygenative homo-coupling of benzyl alcohols holds great promise to build up bibenzyl motifs in organic synthesis,yet it remains a grand challenge in selectivity and activity control.Herein,we first disco...The direct deoxygenative homo-coupling of benzyl alcohols holds great promise to build up bibenzyl motifs in organic synthesis,yet it remains a grand challenge in selectivity and activity control.Herein,we first discovered that iron carbide catalysts displayed high efficiency and selectivity in the catalytic deoxygenative homo-coupling of benzyl alcohols into bibenzyls using H_(2)as the reductant.Ir-promoted Fe0@Fe_(5)C_(2)gave the best performance among the investigated catalysts,and a broad scope of substrates with diverse functional groups could be smoothly converted into bibenzyls,with the yield up to 85%.In addition,in the presence of alkenes,three-component coupling reactions between alcohols and alkenes were also for the first time achieved to construct more complex multi-ring molecules.The radical-trapping experiment and FTIR measurements revealed the radical nature of the reaction and the significantly promoted C–O bond activation after carbonization,respectively.This work will provide guidelines for the rational design of efficient and selective catalysts for the alcohol-involved carbon-carbon coupling reactions.展开更多
Homojunction engineering is a promising modification strategy to improve charge carrier separation and photocatalytic performance of carbon nitrides.Leveraging intrinsic heptazine/triazine phase and face-to-face conta...Homojunction engineering is a promising modification strategy to improve charge carrier separation and photocatalytic performance of carbon nitrides.Leveraging intrinsic heptazine/triazine phase and face-to-face contact,crystalline C_(3)N_(5)(CC3N5)was combined with protonated g-C_(3)N_(4)(pgCN)through electrostatic self-assembly to achieve robust 2D/2D homojunction interfaces.The highest photocatalytic performance was obtained through crystallinity and homojunction engineering,by controlling the pgCN:CC3N5 ratio.The 25:100 pgCN:CC3N5 homo-junction(25CgCN)had the highest hydrogen production(1409.51 μmol h^(-1))and apparent quantum efficiency(25.04%,420 nm),8-fold and 180-fold higher than CC3N5 and pgCN,respectively.This photocatalytic homojunction improves benzaldehyde and hydrogen production activity,retaining 89%performance after 3 cycles(12 h)on a 3D-printed substrate.Electron paramagnetic resonance demonstrated higher·OH,·O_(2) and hole production of irradiated 25CgCN,attributed to crystallinity and homojunction interaction.Thus,electrostatic self-assembly to couple CC3N5 and pgCN in a 2D/2D homojunction interface ameliorates the performance of multifunctional solar-driven applications.展开更多
The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry.In this study,we present a straightforward solvothermal strategy...The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry.In this study,we present a straightforward solvothermal strategy for fabricating a defect-engineered ZrO_(2)/UiO-66-NH_(2)hybrid material with abundant oxygen vacancies,enabling the visible-light-driven oxidation of benzyl alcohol to benzaldehyde.By optimizing the solvothermal treatment duration,the composite(UiO-66-NH_(2)-2h)achieves a 74.1%conversion of benzyl alcohol with>99%selectivity toward benzaldehyde under mild conditions,substantially out-performing pristine UiO-66-NH_(2).Structural and mechanistic studies reveal that the solvothermal process induces the in situ formation of ultrasmall,uniformly dispersed ZrO_(2)nanoparticles(~2.3 nm)within the MOF matrix,while simultaneously generating abundant oxygen vacancies,as confirmed by XPS,EPR,and HRTEM analyses.The defect-mediated electronic structure of the ZrO_(2)/UiO-66-NH_(2)hybrid enhances visible-light absorption,facilitates charge carrier separation,and pro-motes efficient activation of O_(2)into superoxide radicals(·O_(2)^(−)),the primary reactive species.Transient photocurrent measure-ments and electrochemical impedance spectroscopy further verify the improved charge separation efficiency.The synergistic interplay between oxygen vacancies and the intimate ZrO_(2)/UiO-66-NH_(2)interface provides a unique defect-mediated charge transfer pathway,distinguishing this system from conventional heterojunctions.This study demonstrates a facile,one-step approach to integrate defect engineering with interfacial hybridization in MOF-based photocatalysts,off ering a scalable route for solar-driven organic synthesis.展开更多
A biodegradable and green organic compound octadecyl dimethyl benzyl amm-onium chloride(ODBAC)was used as an efficient inhibitor for cold rolled steel(CRS)in phosphoric acid(H_(3)PO_(4)).The mechanism of adsorption an...A biodegradable and green organic compound octadecyl dimethyl benzyl amm-onium chloride(ODBAC)was used as an efficient inhibitor for cold rolled steel(CRS)in phosphoric acid(H_(3)PO_(4)).The mechanism of adsorption and film formation of ODBAC on CRS was studied through experimental and theoretical calculations.The weight loss method shows that the inhibition efficiency of ODBAC can reach 92.01%at a concentration of 10 mg·L^(-1).The adsorption of ODBAC on the CRS surface conforms to the Langmuir isotherm model,which is a mixed adsorption mainly based on physical adsorption.The X-ray photoelectron spectroscopy(XPS)and contact angle results confirmed the existence of the ODBAC film and steel surface's hydrophobicity has been significantly enhanced.Electrochemical test results reveal that the film's formation mainly inhibits the cathodic corrosion reaction and effectively increases the charge transfer resistance.Quantum chemical calculations have found that N18 in ODBAC and C24 and C25 on the benzene ring are the key active adsorption sites.Molecular dynamics simulation results indicate that ODBAC can sharply reduce the free fraction volume to 8%and inhibit the diffusion of corrosion particles,meaning that the formed ODBAC film makes it difficult for corrosion particles to penetrate,thus improving the corrosion resistance of CRS in H_(3)PO_(4).展开更多
文摘A highly efficient benzylation of arenes and heteroarenes catalyzed by HfCl4/HfO2 has been developed. Broad scope of benzylation reagents have been used in this process with high yields under mild condition. Additionally, the HfO2 can be re-used after the reaction. ？2009 Xin Qin Gao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
文摘Selective formation of pharmaceutical intermediates like diphenylmethane, dimethyldiphenylmethane, benzyl toluene and benzoic acid by liquid phase, toluene benzylation with benzyl chloride as a benzylating agent, was systematically studied over plane clay （K-10, montmorillonite）, plane H-Beta, plane MFI structured titanosilicate （TS-1） and heteropoly acids [HPA, namely dodecatungstophosphoric acid [H3PO4.12WOa-xH2O] （TPA）, dodeca-molybdo phosphoric acid ammonium salt hydrate [H12Mo12N3040P＋aq] （DMAA）, sodium tungstate hydrated purified [Na12WO4.2H2O] （STH）] supported on clay, H-beta and TS-1. The 20%TPA/Clay, 30%TPA/H-Beta and 30%TPA/TS-1, were observed to be the best catalyst samples over plane clay, plane H-Beta and plane TS-1. The catalyst samples are compared with respect to benzyl chloride conversion and selectivities for diphenylmethane, dimethyl-diphenylmethane, benzyl toluene and benzoic acid. The reaction follows the pseudo-first order rate power law model. The apparent rate constants are calculated and compared with the reported ones.
基金support from the National Natural Science Foundation of China(Nos.21971224,22071222,22171249)111 Project(No.D20003)+3 种基金the Key Research Projects of Universities in Henan Province(No.21A150053)the Natural Science Foundation of Henan Province(No.202300410375)China Postdoctoral Science Foundation(No.2021M692906)Henan Postdoctoral Foundation(No.202003014).
文摘An SN2-based photochemical strategy using dithiocarbamate anion as catalyst was developed for the activation of benzyl halides,which are extremely challenging to be applied as radical precursors in visible light photocatalysis.With this transition-metal-free and oxidant-free protocol,the benzylation(or cyanomethylation)of various heterocycles including quinoxalin-2(1H)-ones,coumarin,2-phenyl-2H-indazole,1-methyl-5-phenylpyrazin-2(1H)-one,1-(fluoromethyl)cinnolin-4(1H)-one,and 2,4-dibenzyl-1,2,4-triazine-3,5(2H,4H)-dione could be realized(46 examples,up to 98%yield).Importantly,some biologically relevant 3-benzylquinoxalin-2(1H)-ones were also be synthesized under mild conditions.
基金support from National Science Foundation of China(Nos.03772648 and 30721005)Knowledge Innovation Program of the Chinese Academy of Sciences(No.06G8031014)
文摘A new debenzylation of benzyl esters by silica-supported sodium hydrogen sulfate is described. The debenzylation could be achieved selectively and efficiently in good to excellent yields without affecting sensitive functional groups such as nitro, unsaturated bonds, and ethyl ester.
基金Supported by the Science and Technology Program of Guangzhou,China(201804010172)National Natural Science Foundation of China(21808040,21706031,21276052,21776049)Science and Technology Planning Project of Guangdong Province,China(2012A090300006)
文摘The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH3 atmosphere with different time. The resultant zeolites were characterized by a complementary combination of X-ray power diffraction(XRD), scanning electron microscopy(SEM),transmission electron microscopy(TEM), pyridine-IR spectroscopy and N2 adsorption–desorption isotherms. The analyses showed that the nitridation didn’t destroy the crystallinity and specific surface area of zeolites, and the acidity of zeolites can be tailored by tuning the time of nitridation, resulting in the different concentration ratios of Br?nsted-to-Lewis(B/L) acid sites. Moreover, the nitrided zeolites exhibited high selectivity to 2-benzyl-1,3,5-trimethylbenzene than parent silica pillared MFI zeolite nanosheets in benzylation of mesitylene with benzyl alcohol. A balance between Br?nsted acid sites and Lewis acid sites can inhibit the self-etherification of benzyl alcohol and enhance the selectivity of alkylated product. These experimental data implied that nitridation was an effective method to modulate the acidity of zeolites and the synergy between Br?nsted acid sites and Lewis acid sites was a decisive factor to determine the selectivity.
文摘In the presence of Nafion/SiO2 nanocomposite catalyst, the benzylation of aromatic compounds with benzyl chloride proceeded to afford diphenylmethane derivatives in high yields. The catalyst showed high catalytic activity not only for electron-rich aromatic compounds, but also for electron-poor aromatic compounds. Under identical conditions, the self-benzylation of benzyl chloride, and dibenzylation and/or multi-benzylation of aromatic compounds were negligible.
文摘An efficient BF3.OEt2-promoted benzylation of arenes and heteroarenes with various benzyl ether derivatives has been developed. This method provided alternative access to valuable diarylmethane in good yields under mild conditions via an easy work-up procedure.
基金financial support from University of South China。
文摘Herein,we have developed a sustainable linear paired electrolysis strategy for the redox-neutral benzylation of N-heteroarenes with benzyl halides using solid ion resin as the recyclable electrolyte.This method sufficiently utilizes both cathodic and anodic reactions to produce a variety of benzylated Nheteroarenes,features high atom-and step-economy,excellent energy efficiency,operational simplicity,good functional group tolerance,mild conditions and no requirement of sacrifice reagent and base additive.Importantly,the inexpensive and commercially available solid ion resin electrolyte was validated in both gram-scale synthesis and electrolyte cycling experiment.We hope this strategy not only provides a sustainable synthetic strategy for benzylated compounds but also develops the further utilization of ion resin in electrosynthesis as well as linear paired electrolysis.
文摘The development of sustainable and efficient synthetic methodologies for high-valued chemicals from renewable resources is one of the principal aims of chemical industries.Herein,we document the combination of photocatalytic PCET and SCS-enabled direct C-H benzylation of N-heteroarenes with benzaldehydes as the benzyl sources.Avariety of benzylated N-heteroarenes was obtained in moderate to excellent yields at room temperature under metal-,oxidant-free and mild conditions in continuous-flow mode.Mechanistic studies indicated that this benzylation proceeded via PCET activation of benzaldehydes to yield ketyl radicals,the addition of the ketyl radicals to N-heteroarenes to form C-C(OH)bonds,the SCS cleavage to produce benzylic radical and HAT process to deliver the benzylated products.
基金the University of Science and Technology of China and National Natural Science Foundation of China(Grant Nos.21925111,21790333,21702197 and 21672199)for generous and continuous financial support.
文摘Transition-metal mediated activation of inert chemical bonds is an ongoing topic in homogeneous catalysis.In view of the abundance and accessibility of alkylarenes and benzylamines,the use of them as benzyl source in catalytic benzylation reactions via benzylic C-H and C-N bond activation is highly desirable.Indeed,compared with the traditional approaches with benzyl halide as the substrates,benzylation reactions via C-H and C-N bond cleavage provide more efficient,atom-economic strategies to access myriads of synthetically important molecules.In this account,our group's efforts on catalytic benzylation reactions via directed C-H activation,nondirected C-H activation and C-N bond activation are summarized.
文摘The benzylation and allylation of 4-nitrobenzaldehyde (1) could be controlled chemoselectively by using different phase transfer catalyst (FTC) and different metal catalysts. And then, benzylation and allylation of 1 with various organic halides has been realized in high yields in aqueous media.
文摘Polysaceharide is a polyhydroxyl maeromolecular compound. Owing to the influence of the intermolecular and intramolecular hydrogenbonds and difficulty in achieving reaction in solution, it is difficult to obtain products of its complete or selective substitution in the research of polysaccharide modification or structure. The
基金This work was supported by the Jiangxi Provincial Department of Science and Technology Fund(20192BAB213007)the Jiangxi Provincial Education Department Science Fund(GJJ201424)the Key Laboratory of Jiangxi University for Functional Materials Chemistry(No.FMCyl31007005).
文摘α-Aryl-α,α-difluoroacetophenones(DFAPs)are developed as a new class of difluorobenzylation reagents that can be facilely prepared from readily available and cheap starting materials.In situ carbon-carbon bond cleavage of electron-deficient DFAPs gives difluorobenzyl carbanions that undergo base-catalyzed nucleophilic addition to isatins.
文摘Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition.In this study,a series of bimetallic nickel-iron phosphide(Ni_(x)Fe_(2-x)P,where 0<x<2)cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus(RP)for the photocatalytic selective oxidation of benzyl alcohol(BA)coupled with hydrogen production.The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H_(2)yield.The RP regulated by bimetallic phosphide cocatalysts(Ni_(x)Fe_(2-x)P)demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts(Ni_(2)P and Fe2P).In particular,the RP regulated by Ni_(1.25)Fe_(0.75)P exhibited the best photocatalytic performance.In addition,experimental and theoretical calculations further illustrated that Ni_(1.25)Fe_(0.75)P,with the optimized electronic structure,possessed good electrical conductivity and provided strong adsorption and abundant active sites,thereby accelerating electron migration and lowering the reaction energy barrier of RP.This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.
文摘A general metal-free photochemcial oxidation of benzylic C—H bonds has been successfully accomplished via a hydrogen atom transfer(HAT)process.A range of high value-added aromatic ketones were facilely synthesized with high chemoselectivity under mild conditions.Moreover,the mild conditions by using air as the oxidant render the developed proto-col more ecofriendly and environmentally sustainable.
文摘Ni_(2)CoS_(4)was prepared by the liquid‑phase method and applied to the benzyl alcohol electro‑oxidation reaction(BAOR),demonstrating excellent catalytic activity[with a current density of 271 mA·cm^(-2)at 1.40 V(vs RHE)]and long‑term stability.The S‑anion effect can regulate the charge distribution on the catalyst surface,thereby enhancing the additional adsorption capacity of OH-at the Co sites.By combining material characterization and theoretical calculations,it can be observed that this process can increase the concentration of the OH^(*)intermediate,accelerate the activation process of the Ni site,and ultimately achieve an improvement in overall activity and stability.
文摘The direct deoxygenative homo-coupling of benzyl alcohols holds great promise to build up bibenzyl motifs in organic synthesis,yet it remains a grand challenge in selectivity and activity control.Herein,we first discovered that iron carbide catalysts displayed high efficiency and selectivity in the catalytic deoxygenative homo-coupling of benzyl alcohols into bibenzyls using H_(2)as the reductant.Ir-promoted Fe0@Fe_(5)C_(2)gave the best performance among the investigated catalysts,and a broad scope of substrates with diverse functional groups could be smoothly converted into bibenzyls,with the yield up to 85%.In addition,in the presence of alkenes,three-component coupling reactions between alcohols and alkenes were also for the first time achieved to construct more complex multi-ring molecules.The radical-trapping experiment and FTIR measurements revealed the radical nature of the reaction and the significantly promoted C–O bond activation after carbonization,respectively.This work will provide guidelines for the rational design of efficient and selective catalysts for the alcohol-involved carbon-carbon coupling reactions.
基金the financial support provided by the Ministry of Higher Education(MOHE)Malaysia under the Fundamental Research Grant Scheme(FRGS)(Ref no:FRGS/1/2020/TK0/XMU/02/1)The authors would like to thank the Ministry of Science,Technology and Innovation(MOSTI)Malaysia under the Strategic Research Fund(SRF-APP NanoMalaysia BICEP Project 4,S.22015)+5 种基金The authors gratefully acknowledge Agilent Technologies Malaysia Sdn.Bhd.for their contribution through chromatography.This research was supported by the National Natural Science Foundation of China(Ref no:22202168)Guangdong Basic and Applied Basic Research Foundation(Ref no:2021A1515111019)We would also like to acknowledge the financial support from the State Key Laboratory of Physical Chemistry of Solid Surfaces,Xiamen University(Ref.no:2023X11)The authors are thankful to the Embassy of the People's Republic of China in Malaysia for the financial support(Grant no:EENG/0045)This work was also funded by Xiamen University Malaysia Investigatorship Grant(Grant no:IENG/0038)Xiamen University Malaysia Research Fund(ICOE/0001 and XMUMRF/2021-C8/IENG/0041).
文摘Homojunction engineering is a promising modification strategy to improve charge carrier separation and photocatalytic performance of carbon nitrides.Leveraging intrinsic heptazine/triazine phase and face-to-face contact,crystalline C_(3)N_(5)(CC3N5)was combined with protonated g-C_(3)N_(4)(pgCN)through electrostatic self-assembly to achieve robust 2D/2D homojunction interfaces.The highest photocatalytic performance was obtained through crystallinity and homojunction engineering,by controlling the pgCN:CC3N5 ratio.The 25:100 pgCN:CC3N5 homo-junction(25CgCN)had the highest hydrogen production(1409.51 μmol h^(-1))and apparent quantum efficiency(25.04%,420 nm),8-fold and 180-fold higher than CC3N5 and pgCN,respectively.This photocatalytic homojunction improves benzaldehyde and hydrogen production activity,retaining 89%performance after 3 cycles(12 h)on a 3D-printed substrate.Electron paramagnetic resonance demonstrated higher·OH,·O_(2) and hole production of irradiated 25CgCN,attributed to crystallinity and homojunction interaction.Thus,electrostatic self-assembly to couple CC3N5 and pgCN in a 2D/2D homojunction interface ameliorates the performance of multifunctional solar-driven applications.
基金the National Natural Sci-ence Foundation of China(Nos.22271038,22378038,22172012)C.P.thanks Dalian Science and Technology Innovation Fund(No.2024JJ12CG033)+1 种基金C.P.and Z.S thank State Key Laboratory of Heavy Oil Processing(Nos.WX20230149,SKLHOP202402005)Y.-Y.L.thanks the Guangxi Key Laboratory of Information Materials,Guilin University of Electronic Technology(No.231019-K).
文摘The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry.In this study,we present a straightforward solvothermal strategy for fabricating a defect-engineered ZrO_(2)/UiO-66-NH_(2)hybrid material with abundant oxygen vacancies,enabling the visible-light-driven oxidation of benzyl alcohol to benzaldehyde.By optimizing the solvothermal treatment duration,the composite(UiO-66-NH_(2)-2h)achieves a 74.1%conversion of benzyl alcohol with>99%selectivity toward benzaldehyde under mild conditions,substantially out-performing pristine UiO-66-NH_(2).Structural and mechanistic studies reveal that the solvothermal process induces the in situ formation of ultrasmall,uniformly dispersed ZrO_(2)nanoparticles(~2.3 nm)within the MOF matrix,while simultaneously generating abundant oxygen vacancies,as confirmed by XPS,EPR,and HRTEM analyses.The defect-mediated electronic structure of the ZrO_(2)/UiO-66-NH_(2)hybrid enhances visible-light absorption,facilitates charge carrier separation,and pro-motes efficient activation of O_(2)into superoxide radicals(·O_(2)^(−)),the primary reactive species.Transient photocurrent measure-ments and electrochemical impedance spectroscopy further verify the improved charge separation efficiency.The synergistic interplay between oxygen vacancies and the intimate ZrO_(2)/UiO-66-NH_(2)interface provides a unique defect-mediated charge transfer pathway,distinguishing this system from conventional heterojunctions.This study demonstrates a facile,one-step approach to integrate defect engineering with interfacial hybridization in MOF-based photocatalysts,off ering a scalable route for solar-driven organic synthesis.
基金support from National Natural Science Foundation of China(52161016)Joint Key Project of Agricultural Fundamental Research in Yunnan Province(202101BD070001-017)+2 种基金Yunnan Provincial Academician Workstation(202305AF150009)Special Project of“Top Young Talents”of Yunnan Ten Thousand Talents Plan(51900109)Special Project of“Leading Talents of Industrial Technology”of Yunnan Ten Thousand Talents Plan(80201408)are acknowledged.
文摘A biodegradable and green organic compound octadecyl dimethyl benzyl amm-onium chloride(ODBAC)was used as an efficient inhibitor for cold rolled steel(CRS)in phosphoric acid(H_(3)PO_(4)).The mechanism of adsorption and film formation of ODBAC on CRS was studied through experimental and theoretical calculations.The weight loss method shows that the inhibition efficiency of ODBAC can reach 92.01%at a concentration of 10 mg·L^(-1).The adsorption of ODBAC on the CRS surface conforms to the Langmuir isotherm model,which is a mixed adsorption mainly based on physical adsorption.The X-ray photoelectron spectroscopy(XPS)and contact angle results confirmed the existence of the ODBAC film and steel surface's hydrophobicity has been significantly enhanced.Electrochemical test results reveal that the film's formation mainly inhibits the cathodic corrosion reaction and effectively increases the charge transfer resistance.Quantum chemical calculations have found that N18 in ODBAC and C24 and C25 on the benzene ring are the key active adsorption sites.Molecular dynamics simulation results indicate that ODBAC can sharply reduce the free fraction volume to 8%and inhibit the diffusion of corrosion particles,meaning that the formed ODBAC film makes it difficult for corrosion particles to penetrate,thus improving the corrosion resistance of CRS in H_(3)PO_(4).
