Acid catalysis,one of the most important industrial processes,suffers from the toxicity,corrosion and recyclability problems of conventional homogeneous acid catalysts.Thus,the development of green heterogeneous acid ...Acid catalysis,one of the most important industrial processes,suffers from the toxicity,corrosion and recyclability problems of conventional homogeneous acid catalysts.Thus,the development of green heterogeneous acid catalysts becomes the focus of fundamental research and industrial catalysis.As a class of discrete anionic metal-oxygen clusters with tunable structure at the molecular and atomic scales,polyoxometalates(POMs)benefit from their super strong Br?nsted acidity,high proton mobility,and thermal stability.POMs-based heterogeneous catalysts have been used as the potential green alternatives to conventional homogeneous acid catalysts.In this review,we summarize recent progress on the design strategies of the POMs-based heterogeneous catalysts and their catalytic properties in acid-catalyzed reactions,where they are combined with functionalized cations,modified through covalent interactions,supported onto the non-precious metal support,and introduced into the framework of porous polymers.The design,functional strategies and catalytic performance of these POMs-based heterogeneous catalysts in specific acid-catalyzed reactions are emphasized.展开更多
Mesoporous MCM-41 supported Schiff base and Cu SO4· 5H2 O shows high catalytic activity in the cyclocondensation of mercaptoacetic acid with imines（or aldehydes and amines） to afford pharmaceutically important ...Mesoporous MCM-41 supported Schiff base and Cu SO4· 5H2 O shows high catalytic activity in the cyclocondensation of mercaptoacetic acid with imines（or aldehydes and amines） to afford pharmaceutically important thiazolidinone derivatives. The catalytic reactions involving twocomponents or three-components afforded the desired product in high yields（up to 98% and 99%）.Moreover, the catalyst works well with respect to recyclability, giving the product in 85% and 83% yields after recycling six times.展开更多
Photoinduced[2+2]cycloaddition of biomass-derived cycloolefin is a promising approach to synthesize high-energy bio-fuels,however,the conversion efficiency and selectivity are still low.Herein,we provide an acid-promo...Photoinduced[2+2]cycloaddition of biomass-derived cycloolefin is a promising approach to synthesize high-energy bio-fuels,however,the conversion efficiency and selectivity are still low.Herein,we provide an acid-promoted photocycloaddition approach to synthesize a new kind of spiral fuel from biomass-derived cyclohexanone (CHOE) and camphene (CPE).BrΦnsted acids show higher catalytic activity than Lewis acids,and acetic acid (HOAc) possesses the best catalytic performance,with CHOE conversion up to 99.1%.Meanwhile,the HOAc-catalytic effect has been confirmed for[2+2]photocycloaddition of other biomass-derived ketenes and olefins.The catalytic mechanism and dynamics have been investigated,and show that HOAc can bond with C=O groups of CHOE to form H–CHOE complex,which leads to higher light adsorption and longer triplet lifetime.Meanwhile,H–CHOE complex reduces the energy gap between CHOE LUMO and CPE HOMO,shortens the distance of ring-forming atoms,and then decreases the energy barrier (from 103.3 kcal mol^(-1)to 95.8 kcal mol^(-1)) of rate-limiting step.After hydrodeoxygenation,the targeted bio-spiral fuel shows high density of 0.992 g cm^(-3),high neat heat of combustion of 41.89 MJ L^(-1),low kinetic viscosity of 5.69 mm^(2)s^(-1)at 20℃,which is very promising to serve as high-performance aerospace fuel.展开更多
A comprehensive mechanistic study on the chiral phosphoric acid catalyzed an enantioselective asymmetric aza-pinacol rearrangement of 4-chloro-N-(2-(3'-hydroxy-1'-phenylspiro[cyclopentane-1,2'-indolin]-3&#...A comprehensive mechanistic study on the chiral phosphoric acid catalyzed an enantioselective asymmetric aza-pinacol rearrangement of 4-chloro-N-(2-(3'-hydroxy-1'-phenylspiro[cyclopentane-1,2'-indolin]-3'-yl)ethyl)(1a)is investigated at the M06-2X/6-311+G(d,p)level.Our computational results suggest that the whole catalytic cycle proceeds through dehydration of 1a,enantioselective aza-pinacol rearrangement,intramolecular cyclization and catalyst regeneration to deliver the fused indoline product.The aza-pinacol rearrangement is the key stereocontrolling step of the title reaction.The chiral catalyst controls the orientation of the transition states of the enantioselective step through two potential binding sites between the bifunctional chiral phosphate and the aza-ortho-xylylene intermediate.Moreover,theoretical studies identified that the multiple C—H…π,C—H…O,and C—H…N hydrogen bonds and N—H…O^(-)electrostatic interactions between the substrates and the arms as well as functional oxygen anion of the chiral catalyst(R)-4c play a crucial role in determining the stereochemical outcomes.And the strong N—H…O^(-)interaction in the major transition state was found to contribute to the high levels of enantioselectivity.Additionally,the predicted enantiomeric excess(ee)of 89%based on the 6.3 kJ·mol^(–1)energy difference between the enantioselective TS-2-major and TS-2-minor is in agreement with the experimental results of 90%.展开更多
INTRODUCTIONThough potassium salts of rare earth substituted silicotungsticacids were synthesized early in 1971 by R.D.Peacock etc.,sofar the reports about the application of the corresponding acidshave not been found...INTRODUCTIONThough potassium salts of rare earth substituted silicotungsticacids were synthesized early in 1971 by R.D.Peacock etc.,sofar the reports about the application of the corresponding acidshave not been found.We prepared fourteen rare earth substitutedsilicotungstic acids and determined their thermal stability,IRabsorption Spectra and x-ray diffraction spectra.Furthermore,thecatalytic activities of the fourteen heteropoly acids in acid cata-lytic reaction were investigated.Our experimental results demonstrated rare earth substituted silico-tungstic acids have very high catalytic activity in the reaction of展开更多
An efficient new method has been developed to synthesize N2‐alkyl 1,2,3‐triazole products by tol‐uenesulfonic acid （TsOH） catalyzed addition of N1‐Ts substituted 1,2,3‐triazoles to olefins. The reac‐tions of m...An efficient new method has been developed to synthesize N2‐alkyl 1,2,3‐triazole products by tol‐uenesulfonic acid （TsOH） catalyzed addition of N1‐Ts substituted 1,2,3‐triazoles to olefins. The reac‐tions of monosubstituted and unsubstituted triazole substrates with various olefins, including vinyl esters, are explored.展开更多
Metal(Al,Ti,Zr)triflate grafted mesoporous SBA‐15(AlTf/S,TiTf/S,ZrTf/S)samples were synthesizedas inexpensive solid acid materials by a simple one‐pot‐two‐step synthesis methodology.These materials were characteri...Metal(Al,Ti,Zr)triflate grafted mesoporous SBA‐15(AlTf/S,TiTf/S,ZrTf/S)samples were synthesizedas inexpensive solid acid materials by a simple one‐pot‐two‐step synthesis methodology.These materials were characterized by X‐ray diffraction,N2‐sorption,thermogravimetric analysis,Fourier transform infrared spectroscopy(FT‐IR),in‐situ pyridine FT‐IR spectroscopy,and elementalanalysis.ZrTf/S was found to be a highly efficient and reusable solid acid catalyst for ring opening ofepoxides with amines and alcohols and producedβ‐amino alcohols andβ‐alkoxy alcohols respectivelyunder ambient reaction conditions.The ZrTf/S catalyst showed the highest activity,whichwas attributed to its high acidity compared with that of the Ti and Al containing samples.展开更多
Sulfamic acid was proved to be a cost-effective and recyclable catalyst for Friedel-Crafts type reaction of indole withα,β-unsaturated carbonyl compound and benzyl alcohol.Various indoles,α,β-unsaturated carbonyl ...Sulfamic acid was proved to be a cost-effective and recyclable catalyst for Friedel-Crafts type reaction of indole withα,β-unsaturated carbonyl compound and benzyl alcohol.Various indoles,α,β-unsaturated carbonyl compounds and a benzyl alcohol were successfully used in this type of reaction,and the corresponding products were obtained in good to excellent yields.展开更多
Polyoxometalates(POMs)have conducive properties such as controlled Bronsted and Lewis acidity,high thermal stability,nontoxic nature,tunable solubility,and less corrosiveness.POMs have been extensively applied in cata...Polyoxometalates(POMs)have conducive properties such as controlled Bronsted and Lewis acidity,high thermal stability,nontoxic nature,tunable solubility,and less corrosiveness.POMs have been extensively applied in catalytic organic reactions and have an exciting prospect for industrial applications.This review summarized recent progress in the application of POMs as acid catalysts for various organic reactions including C-C bond formation,C-N bond formation,C-O bond formation,heterocyclic synthesis reactions,cyanosilylation and hydrolysis reactions.Various POMs catalysts including heteropoly acids(HPAs)and cationic functionalized HPAs with Bronsted acidity,HPAs supported on non-precious metal support with Bronsted acidity(or both Bronsted and Lewis acidity),transition metal substituted POMs with Lewis acidity were applied in above reactions.This review attempts to provide up-to-date information about POMs acid-catalyzed organic reactions and propose future prospects.展开更多
This paper reports a new strategy for the structural reconstruction of biomass carbon sulfonic acid(BCSA)to its solid superacid counterpart.In this approach,a cheap layered biomass carbon(BC)source is chemically exfol...This paper reports a new strategy for the structural reconstruction of biomass carbon sulfonic acid(BCSA)to its solid superacid counterpart.In this approach,a cheap layered biomass carbon(BC)source is chemically exfoliated by cetyltrimethyl ammonium bromide and then converted to silica-isolated carbon nanosheets(CNSs)by a series of conversion steps.The state of the silica-isolated CNSs and the stacking density of their nanoparticles are regulated by the dehydration temperature.Only the highly isolated and non-crosslinked CNSs with loose particle stacking structures obtained upon dehydration at 250℃ can be turned into superacid sites(with stronger acidity than that of 100%H2 SO4)after sulfonation.This is accompanied by the creation of abundant hierarchical slit pores with high external surface area,mainly driven by the strong hydrogen bonding interactions between the introduced sulfonic acid groups.In typical acid-catalyzed esterification,etherification,and hydrolysis reactions,the newly formed superacid exhibits superior catalytic activity and stability compared to those of common BCSA and commercial Amberlyst-15 catalysts,owing to its good structural stability,highly exposed stable superacidic sites,and abundance of mesoporous/macroporous channels with excellent mass transfer rate.This groundbreaking work not only provides a novel strategy for fabricating bio-based solid superacids,but also overcomes the drawbacks of BCSA,i.e.,unsatisfactory structural stability,acidity,and porosity.展开更多
Sulfamic acid has been used as an efficient catalyst and green alternative for conventional acidic materials to promote the acetolysis reaction of THF to produce 1, 4-diacetoxybutane. This method is also applicable in...Sulfamic acid has been used as an efficient catalyst and green alternative for conventional acidic materials to promote the acetolysis reaction of THF to produce 1, 4-diacetoxybutane. This method is also applicable in the acetolysis of other cyclic ethers, such as methyl substituted THF and tetrahydropyran and 1,4-dioxane which is less reactivity.展开更多
Catalytic asymmetric dearomatization of indoles and alkynes has received much attention in the past decade because this strategy offers an attractive and alternative way for the efficient synthesis of valuable chiral ...Catalytic asymmetric dearomatization of indoles and alkynes has received much attention in the past decade because this strategy offers an attractive and alternative way for the efficient synthesis of valuable chiral polycyclic indolines. However, these reactions have been mostly limited to transition-metal catalysts, and the related chiral Br■nsted acid catalysis has been scarcely reported. Herein, we disclose a chiral phosphoric acid-catalyzed asymmetric dearomatization of indolyl ynamides by direct activation of alkynes. This metal-free method enables the practical and atom-economical construction of an array of valuable chiral polycyclic indolines in moderate to good yields with high enantioselectivities.展开更多
The tacticity of vinyl polymers is a key factor affecting the properties of materials.Recently,organic Brønsted acids have been demonstrated as effective catalysts for the development of highly stereoselective ca...The tacticity of vinyl polymers is a key factor affecting the properties of materials.Recently,organic Brønsted acids have been demonstrated as effective catalysts for the development of highly stereoselective cationic reversible addition-fragmentation chain transfer(RAFT)polymerizations of vinyl ethers,in which the use of RAFT agents could allow the control the molecular weight and tacticity of polymer products simultaneously.However,the effect of RAFT agents on the tacticity-regulation remains elusive and lacks of investigation.In this study,we synthesized four types of RAFT agents and evaluated their influence in the stereoselective cationic polymerization of isobutyl vinyl ether in the presence of PADI as a Brønsted acid catalyst,which unveils that the Z group of RAFT agents could not only affect the polydispersity of the products,but also exert a profound effect on the stereoselectivity.After extensive screening of the RAFT agents,high stereoregularity(isotacticity,90%m)was obtained when using dithiocarbonate ester-type RAFT agents with a benzyloxy Z group.展开更多
In this paper,sulfonic groups functionalized annealed bio-based carbon microspheres loaded polytetrafluoroethylene(A-BCMSs-SO_(3)H@PTFE)fibers with high activity,high stability,and easy regeneration were successfully ...In this paper,sulfonic groups functionalized annealed bio-based carbon microspheres loaded polytetrafluoroethylene(A-BCMSs-SO_(3)H@PTFE)fibers with high activity,high stability,and easy regeneration were successfully fabricated by a simple method using low-cost raw materials.The characterization results showed that the annealed biomass carbon microspheres derived from waste Camellia oleifera shells were evenly distributed on the polytetrafluoroethylene fibers and the sulfonic groups can be successfully loaded on the surface of annealed biomass carbon microspheres by room temperature sulfonation.Subsequently,the as-prepared A-BCMSs-SO_(3)H@PTFE fibers were applied to the acidcatalyzed synthesis of liquid biofuel 5-ethoxymethylfurfural.The catalytic experiment results indicated that the annealing temperature and time during catalyst preparation have a significant effect on the activity and selectivity of A-BCMSs-SO_(3)H@PTFE fibers.The results of catalytic reaction kinetics showed that the yield of 5-ethoxymethylfurfural can reach more than 60%after 72 h of acid-catalyzed reaction.The stability test showed that the as-prepared A-BCMSs-SO_(3)H@PTFE fibers still maintained a stable acid catalytic activity after four recycles.展开更多
Acid-catalyzed tandem reactions were established by employing a novel class of 2-arylglycerol derivative,5-aryl-1,3-dioxan-5-ol,as versatile 1,3-biselectrophile.In the reactions,5-aryl-1,3-dioxan-5-ol works like atrop...Acid-catalyzed tandem reactions were established by employing a novel class of 2-arylglycerol derivative,5-aryl-1,3-dioxan-5-ol,as versatile 1,3-biselectrophile.In the reactions,5-aryl-1,3-dioxan-5-ol works like atropaldehydes or 2-aryl malondialdehydes,and can react with 2-naphthols andβ-keto amides,allowing the synthesis of 4H-chromenes and 5-aryl-2-pyridinones.High yields,good functional group tolerance,broad substrate scope and simple reaction operation make this protocol attractive.展开更多
Phosphoric acid catalysis is a powerful tool for the construction of new CààC bonds because of its unique LUMO-lowering activity. Theoretical calculations were employed to investigate phosphoric acidcatalyze...Phosphoric acid catalysis is a powerful tool for the construction of new CààC bonds because of its unique LUMO-lowering activity. Theoretical calculations were employed to investigate phosphoric acidcatalyzed asymmetric conjugate addition of indolizines to a,b-unsaturated ketones. The calculation results showed that this transformation proceeds via a reaction pathway involving nucleophilic addition,deprotonation–aromatization, and tautomerization. The computational results showed that deprotonation–aromatization is the rate-determining step and the enantioselectivity-determining step.The S-configured product was preferentially generated via a pathway starting from the s-cis conjugated ketone, whereas the s-trans isomer led to a side product with the R configuration. Non-covalent interaction analysis showed that the enantioselectivity is mainly caused by bond-rotation strain in the transition states of the deprotonation–aromatization step.展开更多
In this study, African crude palm olein (CPO) was used to synthesize biodiesel. The objective was to determine the optimal reaction conditions for the methanolysis of olein. The used CPO had a 5.72% concentration of f...In this study, African crude palm olein (CPO) was used to synthesize biodiesel. The objective was to determine the optimal reaction conditions for the methanolysis of olein. The used CPO had a 5.72% concentration of free fatty acids (FFA);thus, the production of biodiesel was carried out in two stages: 1) esterification using sulfuric acid and 2) transesterification using sodium methoxide. In order to optimize the yield of biodiesel during the transesterification process, a central rotatable design and the response surface methodology were used. The studied variables were: catalyst loading, reaction time and reaction temperature. The analysis of variance showed that the variables with significant effect were the catalyst loading, reaction temperature and reaction time;as well as the catalyst loading*reaction temperature and catalyst loading*reaction time. Results indicate that the optimal reaction conditions during transesterification are: 0.65% catalyst loading (wt/wt<sub>aceite</sub>), reaction time of 135 min and a reaction temperature of 56°C. The optimal reaction conditions during esterification are: 2.5% weight of catalyst, reaction time of 150 min and a reaction temperature of 64.5°C. Under these conditions, a 90% yield of biodiesel was obtained.展开更多
A series of Mg‐Al mixed oxide catalysts are prepared and introduced as efficient irreducible catalysts for the oxidative coupling of alcohols and amines to imine.The structure and surface properties of Mg‐Al oxides ...A series of Mg‐Al mixed oxide catalysts are prepared and introduced as efficient irreducible catalysts for the oxidative coupling of alcohols and amines to imine.The structure and surface properties of Mg‐Al oxides are modulated by changing the Mg/Al ratios,calcination temperature and treatment with probe molecules.Detailed characterization,including X‐ray diffraction,27Al magic angle spinning nuclear magnetic resonance spectroscopy,N2‐adsorption,NH3‐temperature‐programmed desorption,CO2‐temperature‐programmed desorption and X‐ray photoelectron spectroscopy are carried out to determine the physicochemical properties of these catalysts.The Mg‐Al oxides with Mg/Al=3exhibit the highest activity in the reaction,which possess a large number of surface weak basic sites and a relatively small number of weak acidic sites.The role of the acidic and basic sites in the reaction process is systematically investigated,and are shown to serve as adsorption and activation sites for amines and alcohols,respectively.Under the synergistic effect of these acid‐base centers,the oxidative coupling process successfully occurs on the surface of Mg‐Al mixed oxides.Compared with the acidic sites,the weak basic sites play a more important role in the catalytic process.The acidic sites are the catalytic centers for the benzyl alcohol activation,which control the reaction rate of the oxidative coupling reaction.展开更多
Glycerol can be obtained as a by-product during biodiesel manufacture. It is important to convert glycerol to value-added products. Glycerol esterification with acetic acid is one of the most promising approaches for ...Glycerol can be obtained as a by-product during biodiesel manufacture. It is important to convert glycerol to value-added products. Glycerol esterification with acetic acid is one of the most promising approaches for glycerol utilization. It is usually difficult to obtain diacetin with good activity and selectivity. In this work, glycerol esterification with acetic acid over different metal oxides, such as Bi2O3, Sb2O3, SnO2, TiO2, Nb2O5 and Sb2O5, was investigated. It was found that in the six investigated metal oxides, only Sb205 resulted in good activity and selectivity to diacetin. Under the optimized conditions, the glycerol conversion reached 96.8%, and the selectivity to diacetin reached 54.2%, while the selectivity to monoacetin and triacetin was 33.2% and 12.6%, respectively. The catalysts were characterized with FT-IR spectra of adsorbed pyridine, which indicated that in the six investigated metal oxides, only Sb2O5 possessed Bronsted acid sites strong enough to protonate adsorbed pyridine. The good catalytic activity and selectivity to diacetin might be mainly attributable to the Bronsted acid sites of Sb2O5. Reusability tests showed that with 5b205 as catalyst, after six reaction cycles, no significant change in the glycerol conversion and the selectivity to diacetin was observed.展开更多
Sulfamic acid has been proved to be the most efficient and recyclable catalyst in carbamate synthesis from alkylamine and dialkyl carbonate.High selectivity,cost-efficiency and simple product separation were the advan...Sulfamic acid has been proved to be the most efficient and recyclable catalyst in carbamate synthesis from alkylamine and dialkyl carbonate.High selectivity,cost-efficiency and simple product separation were the advantageous features obtained in this process.Sulfamic acid could be reused several times and keep its initial activity in the recycle runs.In addition,sulfamic acid has also exhibited the potential catalytic ability for alkylation of aromatic amines.展开更多
基金supported by the National Natural Nature Science Foundation of China(U1707603,21625101,21521005,21808011,U1507102)the National Key Research and Development Program of China(2017YFB0307303)+1 种基金Beijing Natural Science Foundation(2182047,2202039)the Fundamental Research Funds for the Central Universities(XK1802-6,XK1803-05,XK1902,12060093063)。
文摘Acid catalysis,one of the most important industrial processes,suffers from the toxicity,corrosion and recyclability problems of conventional homogeneous acid catalysts.Thus,the development of green heterogeneous acid catalysts becomes the focus of fundamental research and industrial catalysis.As a class of discrete anionic metal-oxygen clusters with tunable structure at the molecular and atomic scales,polyoxometalates(POMs)benefit from their super strong Br?nsted acidity,high proton mobility,and thermal stability.POMs-based heterogeneous catalysts have been used as the potential green alternatives to conventional homogeneous acid catalysts.In this review,we summarize recent progress on the design strategies of the POMs-based heterogeneous catalysts and their catalytic properties in acid-catalyzed reactions,where they are combined with functionalized cations,modified through covalent interactions,supported onto the non-precious metal support,and introduced into the framework of porous polymers.The design,functional strategies and catalytic performance of these POMs-based heterogeneous catalysts in specific acid-catalyzed reactions are emphasized.
基金the National Natural Science Foundation of China(Nos.21162026,21262034 and 21362036)Doctoral Fund of Xinjiang University(No.BS110111)for financial support,Xinjiang University Analytical&Testing Center for instrumental analyses,and Adamas-beta Chemical Co.,for all chemical reagents
文摘Mesoporous MCM-41 supported Schiff base and Cu SO4· 5H2 O shows high catalytic activity in the cyclocondensation of mercaptoacetic acid with imines（or aldehydes and amines） to afford pharmaceutically important thiazolidinone derivatives. The catalytic reactions involving twocomponents or three-components afforded the desired product in high yields（up to 98% and 99%）.Moreover, the catalyst works well with respect to recyclability, giving the product in 85% and 83% yields after recycling six times.
基金the support from National Key R&D Program of China (2021YFC2103704)the National Natural Science Foundation of China (22222808)+4 种基金the Natural Science Foundation of Shandong Province (ZR2023QB152)the Youth Innovation Team Plan of Shandong Province (2022KJ270)the China National Postdoctoral Program for Innovative Talents (BX20240251)the Aeronautical Science Foundation of China (2023Z073048003)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘Photoinduced[2+2]cycloaddition of biomass-derived cycloolefin is a promising approach to synthesize high-energy bio-fuels,however,the conversion efficiency and selectivity are still low.Herein,we provide an acid-promoted photocycloaddition approach to synthesize a new kind of spiral fuel from biomass-derived cyclohexanone (CHOE) and camphene (CPE).BrΦnsted acids show higher catalytic activity than Lewis acids,and acetic acid (HOAc) possesses the best catalytic performance,with CHOE conversion up to 99.1%.Meanwhile,the HOAc-catalytic effect has been confirmed for[2+2]photocycloaddition of other biomass-derived ketenes and olefins.The catalytic mechanism and dynamics have been investigated,and show that HOAc can bond with C=O groups of CHOE to form H–CHOE complex,which leads to higher light adsorption and longer triplet lifetime.Meanwhile,H–CHOE complex reduces the energy gap between CHOE LUMO and CPE HOMO,shortens the distance of ring-forming atoms,and then decreases the energy barrier (from 103.3 kcal mol^(-1)to 95.8 kcal mol^(-1)) of rate-limiting step.After hydrodeoxygenation,the targeted bio-spiral fuel shows high density of 0.992 g cm^(-3),high neat heat of combustion of 41.89 MJ L^(-1),low kinetic viscosity of 5.69 mm^(2)s^(-1)at 20℃,which is very promising to serve as high-performance aerospace fuel.
基金financially supported by the National Natural Science Foundation of China(21873018,21573036,and21603028)the open project of the Jilin Province Key Laboratory of Organic Functional Molecular Design&Synthesis(130028655)the Northeast Normal University Research Frontier Exploration Program(XDFZ202501)
文摘A comprehensive mechanistic study on the chiral phosphoric acid catalyzed an enantioselective asymmetric aza-pinacol rearrangement of 4-chloro-N-(2-(3'-hydroxy-1'-phenylspiro[cyclopentane-1,2'-indolin]-3'-yl)ethyl)(1a)is investigated at the M06-2X/6-311+G(d,p)level.Our computational results suggest that the whole catalytic cycle proceeds through dehydration of 1a,enantioselective aza-pinacol rearrangement,intramolecular cyclization and catalyst regeneration to deliver the fused indoline product.The aza-pinacol rearrangement is the key stereocontrolling step of the title reaction.The chiral catalyst controls the orientation of the transition states of the enantioselective step through two potential binding sites between the bifunctional chiral phosphate and the aza-ortho-xylylene intermediate.Moreover,theoretical studies identified that the multiple C—H…π,C—H…O,and C—H…N hydrogen bonds and N—H…O^(-)electrostatic interactions between the substrates and the arms as well as functional oxygen anion of the chiral catalyst(R)-4c play a crucial role in determining the stereochemical outcomes.And the strong N—H…O^(-)interaction in the major transition state was found to contribute to the high levels of enantioselectivity.Additionally,the predicted enantiomeric excess(ee)of 89%based on the 6.3 kJ·mol^(–1)energy difference between the enantioselective TS-2-major and TS-2-minor is in agreement with the experimental results of 90%.
文摘INTRODUCTIONThough potassium salts of rare earth substituted silicotungsticacids were synthesized early in 1971 by R.D.Peacock etc.,sofar the reports about the application of the corresponding acidshave not been found.We prepared fourteen rare earth substitutedsilicotungstic acids and determined their thermal stability,IRabsorption Spectra and x-ray diffraction spectra.Furthermore,thecatalytic activities of the fourteen heteropoly acids in acid cata-lytic reaction were investigated.Our experimental results demonstrated rare earth substituted silico-tungstic acids have very high catalytic activity in the reaction of
基金supported by the National Natural Science Foundation of China (21272268 and 21472237)~~
文摘An efficient new method has been developed to synthesize N2‐alkyl 1,2,3‐triazole products by tol‐uenesulfonic acid （TsOH） catalyzed addition of N1‐Ts substituted 1,2,3‐triazoles to olefins. The reac‐tions of monosubstituted and unsubstituted triazole substrates with various olefins, including vinyl esters, are explored.
基金supported by the CAS President’s International Fellowship Initiative (2016PT028)the National Natural Science Foundation of China (21273225 and 21403219)~~
文摘Metal(Al,Ti,Zr)triflate grafted mesoporous SBA‐15(AlTf/S,TiTf/S,ZrTf/S)samples were synthesizedas inexpensive solid acid materials by a simple one‐pot‐two‐step synthesis methodology.These materials were characterized by X‐ray diffraction,N2‐sorption,thermogravimetric analysis,Fourier transform infrared spectroscopy(FT‐IR),in‐situ pyridine FT‐IR spectroscopy,and elementalanalysis.ZrTf/S was found to be a highly efficient and reusable solid acid catalyst for ring opening ofepoxides with amines and alcohols and producedβ‐amino alcohols andβ‐alkoxy alcohols respectivelyunder ambient reaction conditions.The ZrTf/S catalyst showed the highest activity,whichwas attributed to its high acidity compared with that of the Ti and Al containing samples.
基金the financial support from the Doctoral Research Fund of Henan University of Traditional Chinese Medicine
文摘Sulfamic acid was proved to be a cost-effective and recyclable catalyst for Friedel-Crafts type reaction of indole withα,β-unsaturated carbonyl compound and benzyl alcohol.Various indoles,α,β-unsaturated carbonyl compounds and a benzyl alcohol were successfully used in this type of reaction,and the corresponding products were obtained in good to excellent yields.
基金supported by the National Natural Science Foundation of China(No.22001034)Jiangxi Provincial Natural Science Foundation(No.20212BAB213001)the Open Fund of the Jiangxi Province Key Laboratory of Synthetic Chemistry(No.JXSC202008)。
文摘Polyoxometalates(POMs)have conducive properties such as controlled Bronsted and Lewis acidity,high thermal stability,nontoxic nature,tunable solubility,and less corrosiveness.POMs have been extensively applied in catalytic organic reactions and have an exciting prospect for industrial applications.This review summarized recent progress in the application of POMs as acid catalysts for various organic reactions including C-C bond formation,C-N bond formation,C-O bond formation,heterocyclic synthesis reactions,cyanosilylation and hydrolysis reactions.Various POMs catalysts including heteropoly acids(HPAs)and cationic functionalized HPAs with Bronsted acidity,HPAs supported on non-precious metal support with Bronsted acidity(or both Bronsted and Lewis acidity),transition metal substituted POMs with Lewis acidity were applied in above reactions.This review attempts to provide up-to-date information about POMs acid-catalyzed organic reactions and propose future prospects.
基金financial support for this work by the National Natural Science Foundation of China(21690080,21676079,21546010,21690083,21878288)the Strategic Priority Research Program of Chinese Academy of Sciences(XDB17020100)+2 种基金DNL Cooperation Fund CAS(DNL180302)the Natural Science Foundation of Hunan Province(2018JJ3335)the Innovation Platform Open Fund of Hunan College(18K016)~~
文摘This paper reports a new strategy for the structural reconstruction of biomass carbon sulfonic acid(BCSA)to its solid superacid counterpart.In this approach,a cheap layered biomass carbon(BC)source is chemically exfoliated by cetyltrimethyl ammonium bromide and then converted to silica-isolated carbon nanosheets(CNSs)by a series of conversion steps.The state of the silica-isolated CNSs and the stacking density of their nanoparticles are regulated by the dehydration temperature.Only the highly isolated and non-crosslinked CNSs with loose particle stacking structures obtained upon dehydration at 250℃ can be turned into superacid sites(with stronger acidity than that of 100%H2 SO4)after sulfonation.This is accompanied by the creation of abundant hierarchical slit pores with high external surface area,mainly driven by the strong hydrogen bonding interactions between the introduced sulfonic acid groups.In typical acid-catalyzed esterification,etherification,and hydrolysis reactions,the newly formed superacid exhibits superior catalytic activity and stability compared to those of common BCSA and commercial Amberlyst-15 catalysts,owing to its good structural stability,highly exposed stable superacidic sites,and abundance of mesoporous/macroporous channels with excellent mass transfer rate.This groundbreaking work not only provides a novel strategy for fabricating bio-based solid superacids,but also overcomes the drawbacks of BCSA,i.e.,unsatisfactory structural stability,acidity,and porosity.
文摘Sulfamic acid has been used as an efficient catalyst and green alternative for conventional acidic materials to promote the acetolysis reaction of THF to produce 1, 4-diacetoxybutane. This method is also applicable in the acetolysis of other cyclic ethers, such as methyl substituted THF and tetrahydropyran and 1,4-dioxane which is less reactivity.
基金financial support from the National Natural Science Foundation of China(Nos.22125108,22101238,92056104 and 21772161)the China Postdoctoral Science Foundation(No.2020M680087)+3 种基金the Natural Science Foundation of Fujian Province of China(No.2019J02001)the President Research Funds from Xiamen University(No.20720210002)the Fundamental Research Funds for the Central Universities(No.20720202008)NFFTBS(No.J1310024)。
文摘Catalytic asymmetric dearomatization of indoles and alkynes has received much attention in the past decade because this strategy offers an attractive and alternative way for the efficient synthesis of valuable chiral polycyclic indolines. However, these reactions have been mostly limited to transition-metal catalysts, and the related chiral Br■nsted acid catalysis has been scarcely reported. Herein, we disclose a chiral phosphoric acid-catalyzed asymmetric dearomatization of indolyl ynamides by direct activation of alkynes. This metal-free method enables the practical and atom-economical construction of an array of valuable chiral polycyclic indolines in moderate to good yields with high enantioselectivities.
基金supported by the Recruitment Program of Global Experts of China,the National Natural Science Foundation of China(Nos.21602028 and 22371240)Beijing National Laboratory for Molecular Sciences(No.BNLMS201913)100-Talent program of Fujian,Fuzhou University and Xiamen University.
文摘The tacticity of vinyl polymers is a key factor affecting the properties of materials.Recently,organic Brønsted acids have been demonstrated as effective catalysts for the development of highly stereoselective cationic reversible addition-fragmentation chain transfer(RAFT)polymerizations of vinyl ethers,in which the use of RAFT agents could allow the control the molecular weight and tacticity of polymer products simultaneously.However,the effect of RAFT agents on the tacticity-regulation remains elusive and lacks of investigation.In this study,we synthesized four types of RAFT agents and evaluated their influence in the stereoselective cationic polymerization of isobutyl vinyl ether in the presence of PADI as a Brønsted acid catalyst,which unveils that the Z group of RAFT agents could not only affect the polydispersity of the products,but also exert a profound effect on the stereoselectivity.After extensive screening of the RAFT agents,high stereoregularity(isotacticity,90%m)was obtained when using dithiocarbonate ester-type RAFT agents with a benzyloxy Z group.
基金financially supported by the National Natural Science Foundation of China(21966023,21665018)the Natural Science Foundation of Jiangxi Province,China(20171ACB21035)
文摘In this paper,sulfonic groups functionalized annealed bio-based carbon microspheres loaded polytetrafluoroethylene(A-BCMSs-SO_(3)H@PTFE)fibers with high activity,high stability,and easy regeneration were successfully fabricated by a simple method using low-cost raw materials.The characterization results showed that the annealed biomass carbon microspheres derived from waste Camellia oleifera shells were evenly distributed on the polytetrafluoroethylene fibers and the sulfonic groups can be successfully loaded on the surface of annealed biomass carbon microspheres by room temperature sulfonation.Subsequently,the as-prepared A-BCMSs-SO_(3)H@PTFE fibers were applied to the acidcatalyzed synthesis of liquid biofuel 5-ethoxymethylfurfural.The catalytic experiment results indicated that the annealing temperature and time during catalyst preparation have a significant effect on the activity and selectivity of A-BCMSs-SO_(3)H@PTFE fibers.The results of catalytic reaction kinetics showed that the yield of 5-ethoxymethylfurfural can reach more than 60%after 72 h of acid-catalyzed reaction.The stability test showed that the as-prepared A-BCMSs-SO_(3)H@PTFE fibers still maintained a stable acid catalytic activity after four recycles.
基金The National Key Research and Development Project(No.2022YFE0124100)Ordos Key Research and Development Project(No.2022EEDSKJZDZX003)+3 种基金National Natural Science Foundation of China(Nos.21872060,21902054,21761132014,and 22072049)the Open Research Fund(No.2022JYBKF01)of Key Laboratory of Material Chemistry for Energy Conversion and Storage(HUST),Ministry of Education,are acknowledged for the financial supportProgram for HUST Academic Frontier Youth Team(No.2019QYTD06)is also acknowledgedsupported by The Innovation and Talent Recruitment Base of New Energy Chemistry and Device。
文摘Acid-catalyzed tandem reactions were established by employing a novel class of 2-arylglycerol derivative,5-aryl-1,3-dioxan-5-ol,as versatile 1,3-biselectrophile.In the reactions,5-aryl-1,3-dioxan-5-ol works like atropaldehydes or 2-aryl malondialdehydes,and can react with 2-naphthols andβ-keto amides,allowing the synthesis of 4H-chromenes and 5-aryl-2-pyridinones.High yields,good functional group tolerance,broad substrate scope and simple reaction operation make this protocol attractive.
基金supported by the National Natural Science Foundation of China (No. 21772020)the Fundamental Research Funds for the Central Universities (Chongqing University) (No. 106112017CDJXY220007)
文摘Phosphoric acid catalysis is a powerful tool for the construction of new CààC bonds because of its unique LUMO-lowering activity. Theoretical calculations were employed to investigate phosphoric acidcatalyzed asymmetric conjugate addition of indolizines to a,b-unsaturated ketones. The calculation results showed that this transformation proceeds via a reaction pathway involving nucleophilic addition,deprotonation–aromatization, and tautomerization. The computational results showed that deprotonation–aromatization is the rate-determining step and the enantioselectivity-determining step.The S-configured product was preferentially generated via a pathway starting from the s-cis conjugated ketone, whereas the s-trans isomer led to a side product with the R configuration. Non-covalent interaction analysis showed that the enantioselectivity is mainly caused by bond-rotation strain in the transition states of the deprotonation–aromatization step.
文摘In this study, African crude palm olein (CPO) was used to synthesize biodiesel. The objective was to determine the optimal reaction conditions for the methanolysis of olein. The used CPO had a 5.72% concentration of free fatty acids (FFA);thus, the production of biodiesel was carried out in two stages: 1) esterification using sulfuric acid and 2) transesterification using sodium methoxide. In order to optimize the yield of biodiesel during the transesterification process, a central rotatable design and the response surface methodology were used. The studied variables were: catalyst loading, reaction time and reaction temperature. The analysis of variance showed that the variables with significant effect were the catalyst loading, reaction temperature and reaction time;as well as the catalyst loading*reaction temperature and catalyst loading*reaction time. Results indicate that the optimal reaction conditions during transesterification are: 0.65% catalyst loading (wt/wt<sub>aceite</sub>), reaction time of 135 min and a reaction temperature of 56°C. The optimal reaction conditions during esterification are: 2.5% weight of catalyst, reaction time of 150 min and a reaction temperature of 64.5°C. Under these conditions, a 90% yield of biodiesel was obtained.
文摘A series of Mg‐Al mixed oxide catalysts are prepared and introduced as efficient irreducible catalysts for the oxidative coupling of alcohols and amines to imine.The structure and surface properties of Mg‐Al oxides are modulated by changing the Mg/Al ratios,calcination temperature and treatment with probe molecules.Detailed characterization,including X‐ray diffraction,27Al magic angle spinning nuclear magnetic resonance spectroscopy,N2‐adsorption,NH3‐temperature‐programmed desorption,CO2‐temperature‐programmed desorption and X‐ray photoelectron spectroscopy are carried out to determine the physicochemical properties of these catalysts.The Mg‐Al oxides with Mg/Al=3exhibit the highest activity in the reaction,which possess a large number of surface weak basic sites and a relatively small number of weak acidic sites.The role of the acidic and basic sites in the reaction process is systematically investigated,and are shown to serve as adsorption and activation sites for amines and alcohols,respectively.Under the synergistic effect of these acid‐base centers,the oxidative coupling process successfully occurs on the surface of Mg‐Al mixed oxides.Compared with the acidic sites,the weak basic sites play a more important role in the catalytic process.The acidic sites are the catalytic centers for the benzyl alcohol activation,which control the reaction rate of the oxidative coupling reaction.
基金supported by the"Strategic Priority Research Program-Climate Change:Carbon Budget and Related Issues"of the Chinese Academy of Sciences(XDA050102)the National Natural Science Foundation of China(21233008)
文摘Glycerol can be obtained as a by-product during biodiesel manufacture. It is important to convert glycerol to value-added products. Glycerol esterification with acetic acid is one of the most promising approaches for glycerol utilization. It is usually difficult to obtain diacetin with good activity and selectivity. In this work, glycerol esterification with acetic acid over different metal oxides, such as Bi2O3, Sb2O3, SnO2, TiO2, Nb2O5 and Sb2O5, was investigated. It was found that in the six investigated metal oxides, only Sb205 resulted in good activity and selectivity to diacetin. Under the optimized conditions, the glycerol conversion reached 96.8%, and the selectivity to diacetin reached 54.2%, while the selectivity to monoacetin and triacetin was 33.2% and 12.6%, respectively. The catalysts were characterized with FT-IR spectra of adsorbed pyridine, which indicated that in the six investigated metal oxides, only Sb2O5 possessed Bronsted acid sites strong enough to protonate adsorbed pyridine. The good catalytic activity and selectivity to diacetin might be mainly attributable to the Bronsted acid sites of Sb2O5. Reusability tests showed that with 5b205 as catalyst, after six reaction cycles, no significant change in the glycerol conversion and the selectivity to diacetin was observed.
基金the Beijing Forestry University Excellent Young Scientist Fund(No.BLYX200904)National Innovation Experiment Program for University Students(No.091002234)Major State Basic Research Development Program of China(973 Program,No.2010CB732204) are gratefully acknowledged.
文摘Sulfamic acid has been proved to be the most efficient and recyclable catalyst in carbamate synthesis from alkylamine and dialkyl carbonate.High selectivity,cost-efficiency and simple product separation were the advantageous features obtained in this process.Sulfamic acid could be reused several times and keep its initial activity in the recycle runs.In addition,sulfamic acid has also exhibited the potential catalytic ability for alkylation of aromatic amines.
