Indole[2,1-α]isoquinolines are an important class of bioactive molecules and show good antibacterial activity.In the present study,an efficient copper(I)-catalyzed acylation/cyclization has been developed for the con...Indole[2,1-α]isoquinolines are an important class of bioactive molecules and show good antibacterial activity.In the present study,an efficient copper(I)-catalyzed acylation/cyclization has been developed for the construction of indolo[2,1-α]isoquinoline derivatives by utilizing 2-aryl-N-acryloyl indole and benzohydrazide as reactants in the presence of CuI as catalyst and tert-butyl hydroperoxide as oxidant.The present protocol exhibits good functional group tolerance,and a series of acylated indole[2,1-α]isoquinolines were synthesized in moderate to good yields.Radical trapping experiments indicated that the reaction may involve a radical process.展开更多
Mechanistic studies of the cleavage and transformation of unactivated C_(sp3)-H bonds are a significant field of chemistry.Overcoming the inherent low acidity of C-H bonds to activate the inert substrates is challenge...Mechanistic studies of the cleavage and transformation of unactivated C_(sp3)-H bonds are a significant field of chemistry.Overcoming the inherent low acidity of C-H bonds to activate the inert substrates is challenge under mild conditions.And their complex multi-step transformations may also hinder mechanistic understanding.Herein,we perform theoretical calculations and experimental studies to explore the C_(sp3)-H bonds activation and acylation mechanisms of toluene/thioether using the relatively weak base LDA.A synergistic"main and auxiliary"model was revealed involving dual lithium metal by LDA dimers,and the aryl dilithium species as an intermediate base can facilitate C_(sp3)-H activation.This model not only aids in understanding the acidity of unactivated C_(sp3)-H bonds and the nucleophilicity of their conjugate bases for their kinetic control through cooperative interactions,but also predicts unusual kinetic isotope effects(KIE)for newly designed 2-(methylthio)naphthalene that are experimentally validated.This research is expected to provide a crucial scenario for the cleavage and transformation of unactivated C_(sp3)-H bonds and the development of new functionalities for alkali metal reagents.展开更多
A support made of mussel-inspired polydopamine-coated magnetic iron oxide nanoparticles （PD-MNPs） was prepared and characterized. The widely used Aspetyillus niger lipase （ANL） was immobilized on the PD-MNPs （ANL...A support made of mussel-inspired polydopamine-coated magnetic iron oxide nanoparticles （PD-MNPs） was prepared and characterized. The widely used Aspetyillus niger lipase （ANL） was immobilized on the PD-MNPs （ANL@PD-MNPs） with a protein loading of 138 mg/g and an activity recovery of 83.6% under optimized conditions. For the immobilization, the pH and immobilization time were investigated. The pH and thermal and storage stability of the ANL@PD-MNPs significant- ly surpassed those of free ANL. The ANL@PD-MNPs had better solvent tolerance than free ANL. The secondary structure of free ANL and ANL@PD-MNPs was analyzed by infrared spectroscopy, A kinetic study demonstrated that the ANL@PD-MNPs had enhanced enzyme-substrate affinity and high catalytic efficiency. The ANL@PD-MNPs was applied as a biocatalyst for the regioselective acylation of dihydromyricetin （DMY） in DMSO and gave a conversion of 79.3%, which was higher than that of previous reports. The ANL@PD-MNPs retained over 55% of its initial activity after 10 cycles of reuse. The ANL@PD-MNPs were readily separated from the reaction system by a magnet. The PD-MNPs is an excellent support for ANL and the resulting ANL@PD-MNPs displayed good potential for the efficient synthesis of dihydromyricetin-3-acetate by enzymatic regioselective acylation.展开更多
目的:长期运动被推荐作为减肥手段,但对肥胖或超重人群食欲激素的具体影响仍不清晰。为此,通过Meta分析评估长期运动对肥胖或超重群体食欲激素的干预效果。方法:系统检索PubMed、EBSCO、Cochrane Library、Web of Science和Embase从建库...目的:长期运动被推荐作为减肥手段,但对肥胖或超重人群食欲激素的具体影响仍不清晰。为此,通过Meta分析评估长期运动对肥胖或超重群体食欲激素的干预效果。方法:系统检索PubMed、EBSCO、Cochrane Library、Web of Science和Embase从建库至2024年12月的随机对照试验。研究对象为超重或肥胖人群,结局指标为食欲激素(胃饥饿素、酰化胃饥饿素、酪酪肽、胰高血糖素样肽1)。使用Review Manager 5.4和Stata 16软件对纳入文献进行Meta分析。结果:长期运动干预显著提升胃饥饿素(SMD=0.46,P=0.007)和胰高血糖素肽1(SMD=0.43,P=0.04)水平,对酰化胃饥饿素(SMD=-0.18,P=0.39)和酪酪肽(SMD=0.23,P=0.39)的调节作用不显著。结果异质性较高,提示个体差异和干预方案对效果有潜在影响。高强度间歇训练调节食欲激素的效果显著,抗阻运动次之,但具体机制尚不明确。短周期的运动训练对于酪酪肽和胰高血糖素样肽1的影响更加显著,但效果随周期延长逐渐减弱。结论:长期运动通过调节食欲激素对肥胖或超重人群的食欲产生抑制作用,高强度间歇训练和抗阻运动在这一领域表现出独特的干预效果,值得进一步深入研究。展开更多
4-Acylated or 3,4-diacylated caffeic acid phenethyl ester （CAPE） was prepared as prodrug to improve its stability and lipid solubility. Their neuroprotective activities were assessed by H202 model and 6-OHDA model. ...4-Acylated or 3,4-diacylated caffeic acid phenethyl ester （CAPE） was prepared as prodrug to improve its stability and lipid solubility. Their neuroprotective activities were assessed by H202 model and 6-OHDA model. The results showed that target compounds displayed positive abilities to protect PC 12 nerve cells from oxidative stress injury, superior to that of CAPE. Additionally, target compounds showed high blood-brain barrier permeability.展开更多
Silica gel supported aluminium trichloride（SiO2-AlCl3） has been shown to be a mild,efficient,and chemoseiective heterogeneous Lewis acid catalyst for the acylation of aromatic compounds with acid chlorides.The catal...Silica gel supported aluminium trichloride（SiO2-AlCl3） has been shown to be a mild,efficient,and chemoseiective heterogeneous Lewis acid catalyst for the acylation of aromatic compounds with acid chlorides.The catalyst can be reused up to five times after simple washing with ether and is stable（as a bench top catalyst）.展开更多
A series of monosubstituted troxerutin esters have been synthesized by enzyme-catalyzed regioselective acylation of troxerutin in nonaqueous medium.Using divinyl dicarboxylates(CH_2=CH-OOC-(CH_2)_n-COO-CH=CH_2,n = 2,3...A series of monosubstituted troxerutin esters have been synthesized by enzyme-catalyzed regioselective acylation of troxerutin in nonaqueous medium.Using divinyl dicarboxylates(CH_2=CH-OOC-(CH_2)_n-COO-CH=CH_2,n = 2,3,4,7,8,11) featuring different chain length as acyl donors and alkaline protease from Bacillus subtilis as catalyst,troxerutin was regioselective acylated at B ethoxyl group.The results indicated that the regioselectivity of the enzyme-catalyzed acylation was not affected by the chain length o...展开更多
Acylation of 2-methylnaphthalene(2-MN) is a very important reaction in organic synthesis,and the effiency of the continuous reactor is more than one of the batch reactor.Considering that the Friedel–Crafts acylation ...Acylation of 2-methylnaphthalene(2-MN) is a very important reaction in organic synthesis,and the effiency of the continuous reactor is more than one of the batch reactor.Considering that the Friedel–Crafts acylation is a rapid exothermic reaction,in this study,we perform the acylation of 2-MN in a stainless steel microchannel flow reactor,which is characterized by high mass and heat transfer rates.The effect of reactant ratio,mixing temperature,reaction temperature,and reaction time on product yield and selectivity were investigated.Under the optimal conditions,2-methyl-6-propionylnaphthalene(2,6-MPN) was obtained in 85.8% yield with 87.5% selectivity.Compared with the conventional batch system,the continuous flow microchannel reactor provides a more efficient method for the synthesis of 2,6-MPN.展开更多
The regioselective acylation of quercetin catalyzed by a novel thermophilic esterase（APE1547） from the archaeon Aeropyrum pernix K1 was successfully conducted in organic solvents.The effects of acyl donor,substrate ...The regioselective acylation of quercetin catalyzed by a novel thermophilic esterase（APE1547） from the archaeon Aeropyrum pernix K1 was successfully conducted in organic solvents.The effects of acyl donor,substrate ratio,organic solvent,temperature,and water activity were investigated.Under the optimum conditions,a yield of 74% for its mono ester could be achieved in the reaction for about 6 h.With the reaction time extending to about 30 h,the final conversion of quercetin was about 100% and three products were synthesized.展开更多
A novel catalytic system, ZnCl2 supported on alumina, was found to be an efficient and readily available medium for the solvent-free Friedel-Crafts acylation reactions under microwave irradiation. Good yields and high...A novel catalytic system, ZnCl2 supported on alumina, was found to be an efficient and readily available medium for the solvent-free Friedel-Crafts acylation reactions under microwave irradiation. Good yields and high catalytic efficiencies were observed within short reaction times. Comparing with silica gel, alumina was more efficient under the same conditions.展开更多
Methoxyacetophenone(4 MAP) was synthesized by the acylation of anisole with acetic anhydride in the presence of HY zeolite. The addition of an appropriate amount of some solvent such as dichloromethane, chloroform, c...Methoxyacetophenone(4 MAP) was synthesized by the acylation of anisole with acetic anhydride in the presence of HY zeolite. The addition of an appropriate amount of some solvent such as dichloromethane, chloroform, carbon disulfide or chlorobenzene to the reaction system can improve the yield of the acylated product to a certain extent. HY zeolite used can be recovered, and reused after being regenerated, obtaining almost the same yield of 4 MAP as the fresh zeolite.展开更多
A series of aromatic ketones 4-acyl anisole were synthesized with high yield by using carboxylic acids as acylating agents and a HY zeolite as catalyst.
Solid superacid, silica-supported polytrifluoromethanesulfosiloxane (SiO2-Si-SCF3) wasfirstly used in the Friedel-Crafts acylation of ferrocene as a novel catalyst. IR spectra, WAXD andspecific surface area of the sup...Solid superacid, silica-supported polytrifluoromethanesulfosiloxane (SiO2-Si-SCF3) wasfirstly used in the Friedel-Crafts acylation of ferrocene as a novel catalyst. IR spectra, WAXD andspecific surface area of the superacid SiO2-Si-SCF3 were also investigated.展开更多
An efficient palladium-catalyzed electrooxidation C–H acylation reaction of N-nitrosoanilines with α-oxocarboxylic acids was developed. The anodic oxidation of the Pd(Ⅱ) intermediate was found to be the key to comp...An efficient palladium-catalyzed electrooxidation C–H acylation reaction of N-nitrosoanilines with α-oxocarboxylic acids was developed. The anodic oxidation of the Pd(Ⅱ) intermediate was found to be the key to complete the reaction. In this case, the N-nitroso group was observed to be an effective directing group for C–H activation reaction. Moreover, the synthetic transformation of derivatives of natural products(L-menthol, dehydroepiandrosterone, and pregnenolone) was successfully realized. Finally, flow electrochemical synthesis of some substrates was achieved.展开更多
A series of acyls （Ac, Bz and Ts） were introduced regioselectively to the 2-hydroxyl in methyl and ally 3-O-benzyl-α-L-rhamnopyranosides mediated by silver（I） oxide in the presence of a catalytic amount of potass...A series of acyls （Ac, Bz and Ts） were introduced regioselectively to the 2-hydroxyl in methyl and ally 3-O-benzyl-α-L-rhamnopyranosides mediated by silver（I） oxide in the presence of a catalytic amount of potassium iodide in 56-78% yields.展开更多
10β-OH can be acylated cleanly when 7α-OH is also free, and thus a facile access to semisynthesis of 7-epi-paclitaxel was proposed. A 2's, 3's-oxazoline paclitaxel analog was serendipitously synthesized
In this study, a new method of synthesis of polyethylene glycol supported potassium tribromide （PEG KBr3） and its application in acylation and bromination reactions are reported. Ammonium persulphate oxidizes I（Br ...In this study, a new method of synthesis of polyethylene glycol supported potassium tribromide （PEG KBr3） and its application in acylation and bromination reactions are reported. Ammonium persulphate oxidizes I（Br to the corresponding tribromide which is entrapped by polyethylene glycol leading to stable PEG KBr3. The reagent is proved to be highly efficient for the acylation of variety of alcohols and bromination of activated aromatic substrates. The method is a mild, one pot reaction and involves no use of toxic reagents.展开更多
文摘Indole[2,1-α]isoquinolines are an important class of bioactive molecules and show good antibacterial activity.In the present study,an efficient copper(I)-catalyzed acylation/cyclization has been developed for the construction of indolo[2,1-α]isoquinoline derivatives by utilizing 2-aryl-N-acryloyl indole and benzohydrazide as reactants in the presence of CuI as catalyst and tert-butyl hydroperoxide as oxidant.The present protocol exhibits good functional group tolerance,and a series of acylated indole[2,1-α]isoquinolines were synthesized in moderate to good yields.Radical trapping experiments indicated that the reaction may involve a radical process.
基金the National Key Research and Development Program of China(No.2021YFA1500100)the National Natural Science Foundation of China(Nos.92156017 and 21890722)+1 种基金“Frontiers Science Center for New Organic Matter”,Nankai University(No.63181206)Haihe Laboratory of Sustainable Chemical Transformation of Tianjin(No.24HHWCSS00019)for generous financial support。
文摘Mechanistic studies of the cleavage and transformation of unactivated C_(sp3)-H bonds are a significant field of chemistry.Overcoming the inherent low acidity of C-H bonds to activate the inert substrates is challenge under mild conditions.And their complex multi-step transformations may also hinder mechanistic understanding.Herein,we perform theoretical calculations and experimental studies to explore the C_(sp3)-H bonds activation and acylation mechanisms of toluene/thioether using the relatively weak base LDA.A synergistic"main and auxiliary"model was revealed involving dual lithium metal by LDA dimers,and the aryl dilithium species as an intermediate base can facilitate C_(sp3)-H activation.This model not only aids in understanding the acidity of unactivated C_(sp3)-H bonds and the nucleophilicity of their conjugate bases for their kinetic control through cooperative interactions,but also predicts unusual kinetic isotope effects(KIE)for newly designed 2-(methylthio)naphthalene that are experimentally validated.This research is expected to provide a crucial scenario for the cleavage and transformation of unactivated C_(sp3)-H bonds and the development of new functionalities for alkali metal reagents.
基金supported by the National Natural Science Foundation of China(21336002,21222606,21376096)the Key Program of Guangdong Natural Science Foundation(S2013020013049)+1 种基金the Fundamental Research Funds for the Chinese Universities(2015PT002,2015ZP009)the Program of State Key Laboratory of Pulp and Paper Engineering(2015C04)~~
文摘A support made of mussel-inspired polydopamine-coated magnetic iron oxide nanoparticles （PD-MNPs） was prepared and characterized. The widely used Aspetyillus niger lipase （ANL） was immobilized on the PD-MNPs （ANL@PD-MNPs） with a protein loading of 138 mg/g and an activity recovery of 83.6% under optimized conditions. For the immobilization, the pH and immobilization time were investigated. The pH and thermal and storage stability of the ANL@PD-MNPs significant- ly surpassed those of free ANL. The ANL@PD-MNPs had better solvent tolerance than free ANL. The secondary structure of free ANL and ANL@PD-MNPs was analyzed by infrared spectroscopy, A kinetic study demonstrated that the ANL@PD-MNPs had enhanced enzyme-substrate affinity and high catalytic efficiency. The ANL@PD-MNPs was applied as a biocatalyst for the regioselective acylation of dihydromyricetin （DMY） in DMSO and gave a conversion of 79.3%, which was higher than that of previous reports. The ANL@PD-MNPs retained over 55% of its initial activity after 10 cycles of reuse. The ANL@PD-MNPs were readily separated from the reaction system by a magnet. The PD-MNPs is an excellent support for ANL and the resulting ANL@PD-MNPs displayed good potential for the efficient synthesis of dihydromyricetin-3-acetate by enzymatic regioselective acylation.
基金National Natural Science Foundation of China(Grant No.201310061931.8)
文摘4-Acylated or 3,4-diacylated caffeic acid phenethyl ester （CAPE） was prepared as prodrug to improve its stability and lipid solubility. Their neuroprotective activities were assessed by H202 model and 6-OHDA model. The results showed that target compounds displayed positive abilities to protect PC 12 nerve cells from oxidative stress injury, superior to that of CAPE. Additionally, target compounds showed high blood-brain barrier permeability.
文摘Silica gel supported aluminium trichloride（SiO2-AlCl3） has been shown to be a mild,efficient,and chemoseiective heterogeneous Lewis acid catalyst for the acylation of aromatic compounds with acid chlorides.The catalyst can be reused up to five times after simple washing with ether and is stable（as a bench top catalyst）.
基金the Science and Technology hall of Henan Province(No.072300420070No.82102330014)China,for financially supported to this work.
文摘A series of monosubstituted troxerutin esters have been synthesized by enzyme-catalyzed regioselective acylation of troxerutin in nonaqueous medium.Using divinyl dicarboxylates(CH_2=CH-OOC-(CH_2)_n-COO-CH=CH_2,n = 2,3,4,7,8,11) featuring different chain length as acyl donors and alkaline protease from Bacillus subtilis as catalyst,troxerutin was regioselective acylated at B ethoxyl group.The results indicated that the regioselectivity of the enzyme-catalyzed acylation was not affected by the chain length o...
基金Supported by the National Natural Science Foundation of China(91634101)The Project of Construction of Innovative Teams and Teacher Career Development for Universities and Colleges under Beijing Municipality(IDHT20180508)
文摘Acylation of 2-methylnaphthalene(2-MN) is a very important reaction in organic synthesis,and the effiency of the continuous reactor is more than one of the batch reactor.Considering that the Friedel–Crafts acylation is a rapid exothermic reaction,in this study,we perform the acylation of 2-MN in a stainless steel microchannel flow reactor,which is characterized by high mass and heat transfer rates.The effect of reactant ratio,mixing temperature,reaction temperature,and reaction time on product yield and selectivity were investigated.Under the optimal conditions,2-methyl-6-propionylnaphthalene(2,6-MPN) was obtained in 85.8% yield with 87.5% selectivity.Compared with the conventional batch system,the continuous flow microchannel reactor provides a more efficient method for the synthesis of 2,6-MPN.
基金Supported by the National Natural Science Foundation of China(Nos.31070708,21172093 and 20772046)the Natural Science Foundation of Jilin Province,China(No.201115038)
文摘The regioselective acylation of quercetin catalyzed by a novel thermophilic esterase（APE1547） from the archaeon Aeropyrum pernix K1 was successfully conducted in organic solvents.The effects of acyl donor,substrate ratio,organic solvent,temperature,and water activity were investigated.Under the optimum conditions,a yield of 74% for its mono ester could be achieved in the reaction for about 6 h.With the reaction time extending to about 30 h,the final conversion of quercetin was about 100% and three products were synthesized.
文摘A novel catalytic system, ZnCl2 supported on alumina, was found to be an efficient and readily available medium for the solvent-free Friedel-Crafts acylation reactions under microwave irradiation. Good yields and high catalytic efficiencies were observed within short reaction times. Comparing with silica gel, alumina was more efficient under the same conditions.
文摘Methoxyacetophenone(4 MAP) was synthesized by the acylation of anisole with acetic anhydride in the presence of HY zeolite. The addition of an appropriate amount of some solvent such as dichloromethane, chloroform, carbon disulfide or chlorobenzene to the reaction system can improve the yield of the acylated product to a certain extent. HY zeolite used can be recovered, and reused after being regenerated, obtaining almost the same yield of 4 MAP as the fresh zeolite.
文摘A series of aromatic ketones 4-acyl anisole were synthesized with high yield by using carboxylic acids as acylating agents and a HY zeolite as catalyst.
基金We are grateful to the National Natural Science Foundation of China(20362007)for the financial support.
文摘Solid superacid, silica-supported polytrifluoromethanesulfosiloxane (SiO2-Si-SCF3) wasfirstly used in the Friedel-Crafts acylation of ferrocene as a novel catalyst. IR spectra, WAXD andspecific surface area of the superacid SiO2-Si-SCF3 were also investigated.
基金the Guangxi Natural Science Foundation of China (No. 2021GXNSFFA220005)the Central Government Guides Local Science and Technology Development Fund Projects (No. guike ZY21195014)+2 种基金National Natural Science Foundation of China (Nos. 22061003, 22161008, 22161007)middle-aged and young teachers’ basic scientific research ability improvement project of Guangxi (No. RZ1900005748)the Opening Project of Hunan Engineering Laboratory for analyse and Drugs Development of Ethnomedicine in Wuling Mountain (No. hgxy2101) for financial support。
文摘An efficient palladium-catalyzed electrooxidation C–H acylation reaction of N-nitrosoanilines with α-oxocarboxylic acids was developed. The anodic oxidation of the Pd(Ⅱ) intermediate was found to be the key to complete the reaction. In this case, the N-nitroso group was observed to be an effective directing group for C–H activation reaction. Moreover, the synthetic transformation of derivatives of natural products(L-menthol, dehydroepiandrosterone, and pregnenolone) was successfully realized. Finally, flow electrochemical synthesis of some substrates was achieved.
基金financially supported by the National Natural Science Foundation of China(No.30300434)the 0utstanding Youth Foundation of Sichuan Province(No.04ZQ026-039).
文摘A series of acyls （Ac, Bz and Ts） were introduced regioselectively to the 2-hydroxyl in methyl and ally 3-O-benzyl-α-L-rhamnopyranosides mediated by silver（I） oxide in the presence of a catalytic amount of potassium iodide in 56-78% yields.
文摘10β-OH can be acylated cleanly when 7α-OH is also free, and thus a facile access to semisynthesis of 7-epi-paclitaxel was proposed. A 2's, 3's-oxazoline paclitaxel analog was serendipitously synthesized
基金the Department of Science and Technology,DST,New Delhi,India,for fnancial assistance received through a SERC fast track project(No.SR/FTP/CS-100/2007)
文摘In this study, a new method of synthesis of polyethylene glycol supported potassium tribromide （PEG KBr3） and its application in acylation and bromination reactions are reported. Ammonium persulphate oxidizes I（Br to the corresponding tribromide which is entrapped by polyethylene glycol leading to stable PEG KBr3. The reagent is proved to be highly efficient for the acylation of variety of alcohols and bromination of activated aromatic substrates. The method is a mild, one pot reaction and involves no use of toxic reagents.
