A visible light-promoted fast photochemical Wolff rearrangement was developed toward synthesis ofα-substituted amides in continuous flow with the use of a photochemical oscillatory flow reactor(POFR).The control expe...A visible light-promoted fast photochemical Wolff rearrangement was developed toward synthesis ofα-substituted amides in continuous flow with the use of a photochemical oscillatory flow reactor(POFR).The control experiment indicates that a fast process of the Wolff rearrangement(<40 s)is involved.Notably,this protocol does not require excess use of any reactants,and the resultingα-substituted amides could be isolated by recrystallization in good to excellent yields.展开更多
The amide moiety plays an important role as a powerful bioactive backbone,and as the synthetic chemistry community moves toward more sp^(3)-rich scaffolds,alkyl halides have become the feedstock of choice for obtainin...The amide moiety plays an important role as a powerful bioactive backbone,and as the synthetic chemistry community moves toward more sp^(3)-rich scaffolds,alkyl halides have become the feedstock of choice for obtaining carbonylation products.With the development of photoredox catalysis,several aminocarbonylation systems for alkyl halides were developed which usually require transition metal catalysis.Considering the demands for green sustainable chemical synthesis,here we report a metal-free,exogenous catalyst-free aminocarbonylation reaction of alkyl iodides under atmospheric pressure of carbon monoxide.Through a combination of EDA and XAT strategies,the reaction occurs efficiently under only light irradiation at room temperature.展开更多
Chiral N-substituted amino amides and esters are ubiquitous scaffolds in pesticides and pharmaceutical chemicals,but their asymmetric synthesis remains challenging especially for those with multiple chiral centers.In ...Chiral N-substituted amino amides and esters are ubiquitous scaffolds in pesticides and pharmaceutical chemicals,but their asymmetric synthesis remains challenging especially for those with multiple chiral centers.In this study,IR104 from Streptomyces aureocirculatus was identified from 157 wild-type imine reductases for the synthesis of(S)-2-((R)-2-oxo-4-propylpyrrolidin-1-yl)butanamide(antiepileptic drug Brivaracetam)via dynamic kinetic resolution reductive amination from ethyl 3-formylhexanoate and(S)-2-aminobutylamide with high diastereoselectivity.To further improve the catalytic efficiency of IR104,its mutant D191E/L195I/E253S/M258A(M3)was identified by saturation mutagenesis and iterative combinatorial mutagenesis,which exhibited a 102-fold increase in the catalytic efficiency relative to that of wild-type enzyme and high diastereoselectivity(98:2 d.r.).Crystal structural analysis and molecular dynamics simulations provided some insights into the molecular basis for the improved activity of the mutant enzyme.The imine reductase identified in this study could accept chiral amino amides/esters as amino donors for the dynamic kinetic resolution reductive amination of racemicα-substituted aldehydo-esters,expanding the substrate scope of imine reductases in the dynamic kinetic resolution-reductive amination.Finally,IR104-M3 was successfully used for the preparation of Brivaracetam at gram scale.Using this mutant,various N-substituted amino amides/esters with two chiral centers were also synthesized with up to 99:1 d.r.and 96%yields and subsequently converted intoγ-andδ-lactams,providing an efficient protocol for the synthesis of these important compounds via enzymatic dynamic kinetic resolution-reductive amination from simple building blocks.展开更多
Catalytic Michael addition reaction represents a fundamental importance in organic synthetic chemistry.Whereas corresponding conversions toward intrinsically low reactive enamide remains an ongoing challenging.We here...Catalytic Michael addition reaction represents a fundamental importance in organic synthetic chemistry.Whereas corresponding conversions toward intrinsically low reactive enamide remains an ongoing challenging.We herein report a copper-catalyzed conjugate addition of allenes toβ-substituted alkenyl amides,one of the most challenging Michael acceptors.The present method utilizes readily available allenes as the latent carbon-based nucleophiles and simple,commonβ-substituted alkenyl amides as starting materials,unlike previous methods that usually preinstall an activating group to improve the reactivity of amide or uses highly reactive stoichiometric quantities of organometallics.Hence,this approach shows good functional group compatibility and can be implemented under mild reaction conditions with excellent level of chemo-and regioselectivities.展开更多
A highly efficient copper-catalyzed approach to form amide bonds from formamides and carboxylic acids was developed. This protocol shows broad substrate scopes and high yields in the presence of 1 mol% catalyst and 4....A highly efficient copper-catalyzed approach to form amide bonds from formamides and carboxylic acids was developed. This protocol shows broad substrate scopes and high yields in the presence of 1 mol% catalyst and 4.0 equiv, formamides.展开更多
The development of economic and environmentally friendly extractants to recover cobalt metal is required due to the increasing demand for this metal.In this study,solvent extraction of Co（Ⅱ） from aqueous solution u...The development of economic and environmentally friendly extractants to recover cobalt metal is required due to the increasing demand for this metal.In this study,solvent extraction of Co（Ⅱ） from aqueous solution using a mixture of N,N＇-carbonyl difatty amides（CDFAs） synthesised from palm oil as the extractant was carried out.The effects of various parameters such as acid,contact time,extractant concentration,metal ion concentration and stripping agent and the separation of Co（Ⅱ） from other metal ions such as Fe（Ⅱ）,Ni（Ⅱ）,Zn（Ⅲ） and Cd（Ⅱ） were investigated.It was found that the extraction of Co（Ⅱ） into the organic phase involved the formation of 1：1 complexes.Co（Ⅱ） was successfully separated from commonly associated metal ions such as Fe（Ⅱ）,Ni（Ⅱ）,Zn（Ⅲ） and Cd（Ⅱ）.Co（Ⅱ） stripping from the loaded organic phase was studied in aqueous solution.These results are useful to recover Co（Ⅱ） from aqueous solution utilising（CDFAs） as an extractant.展开更多
Four new phenolic amides,4-O-methylgrossamide(1),(E)-2-(4,5-dihydroxy-2-{3-[(4-hydrox-yphenethyl)amino]-3-oxopropyl}-phenyl)-3-(4-hydroxy-3-methoxyphenyl)-N-(4-hydroxyphenethyl)acryl-amide(2),(Z)-lyciumamide C(3),(Z)-...Four new phenolic amides,4-O-methylgrossamide(1),(E)-2-(4,5-dihydroxy-2-{3-[(4-hydrox-yphenethyl)amino]-3-oxopropyl}-phenyl)-3-(4-hydroxy-3-methoxyphenyl)-N-(4-hydroxyphenethyl)acryl-amide(2),(Z)-lyciumamide C(3),(Z)-thoreliamide B(4),together with thirteen known phenolic amides were identified from the stem of Lycium barbarum.The structures of the new compounds were determined by spectroscopic methods.All compounds were evaluated for their anti-cancer activities against human glioma stem cell lines.展开更多
Amides,a series of significant atmospheric nitrogen-containing volatile organic compounds(VOCs),can participate in new particle formation(NPF)throught interacting with sulfuric acid(SA)and organic acids.In this study,...Amides,a series of significant atmospheric nitrogen-containing volatile organic compounds(VOCs),can participate in new particle formation(NPF)throught interacting with sulfuric acid(SA)and organic acids.In this study,we investigated the molecular interactions of formamide(FA),acetamide(AA),N-methylformamide(MF),propanamide(PA),Nmethylacetamide(MA),and N,N-dimethylformamide(DMF)with SA,acetic acid(HAC),propanoic acid(PAC),oxalic acid(OA),and malonic acid(MOA).Global minimum of clusters were obtained through the association of the artificial bee colony(ABC)algorithm and density functional theory(DFT)calculations.The conformational analysis,thermochemical analysis,frequency analysis,and topological analysis were conducted to determine the interactions of hydrogen-bonded molecular clusters.The heterodimers formed a hepta or octa membered ring through four different types of hydrogen bonds,and the strength of the bonds are ranked in the following order:SO-H···O>CO-H···O>N-H···O>C-H···O.We also evaluated the stability of the clusters and found that the stabilization effect of amides with SA is weaker than that of amines with SA but stronger than that of ammonia(NH 3)with SA in the dimer formation of nucleation process.Additionally,the nucleation capacity of SA with amides is greater than that of organic acids with amides.展开更多
Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage mol...Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage molecular weight ranging from 1.02 × 10~6 g/mol to 1.23 ×10~6 g/mol (M_w/M_n= 1.9-2.2) could be prepared utilizing lithium amides derived from diisopropylamine, diethylamine, hexamethyldisilazane,dicyclohexylamine, and 2,2,6,6-tetramethylpiperidine as initiators. The polymerization of acrylonitrile proceeded in a homogeneous manner in N,N-di methyl for mamide and insignificant contribution of side reactions was confirmed.展开更多
A series of novel N-（3-furan-2-yl-l-phenyl-lH-pyrazol-5-yl） amides derivatives were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR and HRMS. All title compounds were evaluated for their...A series of novel N-（3-furan-2-yl-l-phenyl-lH-pyrazol-5-yl） amides derivatives were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR and HRMS. All title compounds were evaluated for their herbicidal and antifungal activities. Preliminary bioassay results indicated that the title compounds showed good to moderate herbicidal activity at 1000 mg/L. Compound 6q presented the best activity against Digitaria sanguinalis （L） Scop., Amaranthus retroflexus L. and Arabidopsis thaliana with an inhibition degree of five. Compound 6d also showed an inhibition degree of five against D. sanguinalis. In addition, at 50 mg/L, most compounds exhibited good in vitro antifungal activity against Sclerotinia sclerotiorum, with compound 6c showing over 90% antifungal activity against S. sclerotiorum and Pellicularia sasakii.展开更多
One undescribedamide,pipermullesine A,twoundescribed isoquinoline alkaloids,pipermullesinesBand C,and six undescribed dipeptides,pipermullamides A–F,along with 28 known compounds,were isolated from the aerial parts o...One undescribedamide,pipermullesine A,twoundescribed isoquinoline alkaloids,pipermullesinesBand C,and six undescribed dipeptides,pipermullamides A–F,along with 28 known compounds,were isolated from the aerial parts of Piper mullesua.The structures of the undescribed compounds were elucidated based on the analysis of 1D and 2D NMR and MS data.Furthermore,the structures of pipermullesines A–Cwere confirmed by single crystal X-ray diffraction analysis.All isolates were evaluated for inhibitory activity against platelet aggregation induced by thrombin(IIa)or platelet-activating factor(PAF).(-)-Mangochinine,pellitorine,and(2E,4E)-N-isobutyl-2,4-dodecadienamide showed weak inhibitory activity against rabbit platelet aggregation induced by PAF,with IC_(50)values of 470.3μg/mL,614.9μg/mL,and 579.7μg/mL,respectively.展开更多
Indium(III) triflate, a trivalent indium reagent, was shown to be a highly-efficient catalyst for the conversion of primary amides to the corresponding nitriles. The successful reactions required 5 mol% of indium(III)...Indium(III) triflate, a trivalent indium reagent, was shown to be a highly-efficient catalyst for the conversion of primary amides to the corresponding nitriles. The successful reactions required 5 mol% of indium(III) triflate, and toluene was proved to be the most suitable solvent. Various amides were subjected to this method, and each produced the corresponding nitriles in excellent yields.展开更多
Based on the structure of compound B51（IC_（50） = 37.4 μM）, which was discovered as hit in a previous virtual screen, a series of methylisoxazole/isothiazole amide derivatives were designed and synthesized as BACE...Based on the structure of compound B51（IC_（50） = 37.4 μM）, which was discovered as hit in a previous virtual screen, a series of methylisoxazole/isothiazole amide derivatives were designed and synthesized as BACE1 inhibitors. The methoxyphenylpyrimidone fragment of B51 was transformed into a methoxyphenylmethylisoxazole/isothiazole moiety to reduce the molecular weight while retaining the ability to fit into the S1＇ and S2＇ subpocket of BACE1 as predicted by docking studies. The effects of BACE1 inhibition and the structure-activity relationships were analyzed. Among all 20 designed compounds, 5t exhibited almost 10-fold improved potency（IC_（50） = 5.33 μM） compared to B51 in the BACE1 inhibition assay. Additionally, it has exhibited ＂rapid binding, slow dissociation＂ kinetics in SPR analysis, suggesting a longer inhibitory effect than B51. All acquired methylisoxazole/isothiazole derivatives were small in size and safe to normal cells, which allow them represent a novel scaffold for BACE1 inhibitor design.展开更多
?β-Unsaturated amides with various substitution pattems at the carbon-carbon double And and nitrogen atom can be reduced to the corresponding saturated amides with high selectivity and yields with NaBH4/BiCl3 system.
Secondary amides are a class of highly stable compounds serving as versatile starting materials,intermediates and directing groups（amido groups） in organic synthesis.The direct deacylation of secondary amides to rel...Secondary amides are a class of highly stable compounds serving as versatile starting materials,intermediates and directing groups（amido groups） in organic synthesis.The direct deacylation of secondary amides to release amines is an important transformation in organic synthesis.Here,we report a protocol for the deacylation of secondary amides and isolation of amines.The method is based on the activation of amides with Tf_2O.followed by addition of organocerium reagents,and acidic work-up.The reaction proceeded under mild conditions and afforded the corresponding amines,isolated as their hydrochloride salts,in good yields.In combination with the C-H activation functionalization methodology,the method is applicable to the functionalization of aniline as well as conversion of carboxylic derivatives to functionalized ketones.展开更多
α,β-Unsaturated primary amides are important intermediates and building blocks in organic synthesis.Herein,we report a ligand-free iron-catalyzed hydroaminocarbonylation of alkynes using NH_(4)HCO_(3)as the ammonia ...α,β-Unsaturated primary amides are important intermediates and building blocks in organic synthesis.Herein,we report a ligand-free iron-catalyzed hydroaminocarbonylation of alkynes using NH_(4)HCO_(3)as the ammonia source,enabling the highly efficient and regioselective synthesis of linearα,β-unsaturated primary amides.Various aromatic and aliphatic alkynes are transformed into the desired linearα,β-unsaturated primary amides in good to excellent yields.Further studies show that using NH_(4)HCO_(3)as the ammonia source is key to obtain good yields and selectivity.The utility of this route is demonstrated with the synthesis of linearα,β-unsaturated amides including vanilloid receptor-1 antagonist TRPV-1.展开更多
Two new amides(E)-N-cinnamoyl-2-methoxypiperidine(1)and(R)-1-(2-oxopyrrolidin-3-yl)-5,6-dihydropyridin-2(1H)-one(2),four new amide glucosides,retrofractosides A-D(3-6),and two new phenylpropanoid glucosides,retrofract...Two new amides(E)-N-cinnamoyl-2-methoxypiperidine(1)and(R)-1-(2-oxopyrrolidin-3-yl)-5,6-dihydropyridin-2(1H)-one(2),four new amide glucosides,retrofractosides A-D(3-6),and two new phenylpropanoid glucosides,retrofractosides E(7)and F(8),together with 24 known compounds(9-32)were isolated from the fruits of Piper retrofractum.The chemical structures of these new compounds were elucidated based on extensive spectroscopic analysis.All of these isolates(1-32)were evaluated for inhibitory activity against mouse platelet aggregation induced by the peptide AYPGKF-NH2.(E)-N-(Tetrahydro-2H-pyran-2-yl)cinnamamide(9)showed a weak inhibitory efect,with an inhibition ratio of 52.0%at a concentration of 150μM.展开更多
A novel aromatic diamine, 1, 2-dihydro-2-（4-aminophenyl）-4-[3-methoxy-4-（4-aminophenoxy）]-2, 3-phthalazin-l-one （OO-DA） containing aza heterocyclic structure was synthesized from the bisphenol-like monomer in tw...A novel aromatic diamine, 1, 2-dihydro-2-（4-aminophenyl）-4-[3-methoxy-4-（4-aminophenoxy）]-2, 3-phthalazin-l-one （OO-DA） containing aza heterocyclic structure was synthesized from the bisphenol-like monomer in two steps and used for preparing new aromatic polyamides with high inherent viscosity of 0.89-1.03 dL.g^-1. The structures of diamine and polymers obtained were confirmed by MS, PT-IR, WAXD and ^1H-NMR. The synthesized polymers exhibited high glass transition temperature in the range of 281-307℃ and good solubility in polar solvents.展开更多
基金financial support from the National Natural Science Foundation of China(No.22208279)Financial support from the Fuzhou University(No.0041/511095)。
文摘A visible light-promoted fast photochemical Wolff rearrangement was developed toward synthesis ofα-substituted amides in continuous flow with the use of a photochemical oscillatory flow reactor(POFR).The control experiment indicates that a fast process of the Wolff rearrangement(<40 s)is involved.Notably,this protocol does not require excess use of any reactants,and the resultingα-substituted amides could be isolated by recrystallization in good to excellent yields.
基金supported by National Key R&D Program of China(No.2023YFA1507500)the International Partnership Program of Chinese Academy of Sciences(No.028GJHZ2023045FN)。
文摘The amide moiety plays an important role as a powerful bioactive backbone,and as the synthetic chemistry community moves toward more sp^(3)-rich scaffolds,alkyl halides have become the feedstock of choice for obtaining carbonylation products.With the development of photoredox catalysis,several aminocarbonylation systems for alkyl halides were developed which usually require transition metal catalysis.Considering the demands for green sustainable chemical synthesis,here we report a metal-free,exogenous catalyst-free aminocarbonylation reaction of alkyl iodides under atmospheric pressure of carbon monoxide.Through a combination of EDA and XAT strategies,the reaction occurs efficiently under only light irradiation at room temperature.
文摘Chiral N-substituted amino amides and esters are ubiquitous scaffolds in pesticides and pharmaceutical chemicals,but their asymmetric synthesis remains challenging especially for those with multiple chiral centers.In this study,IR104 from Streptomyces aureocirculatus was identified from 157 wild-type imine reductases for the synthesis of(S)-2-((R)-2-oxo-4-propylpyrrolidin-1-yl)butanamide(antiepileptic drug Brivaracetam)via dynamic kinetic resolution reductive amination from ethyl 3-formylhexanoate and(S)-2-aminobutylamide with high diastereoselectivity.To further improve the catalytic efficiency of IR104,its mutant D191E/L195I/E253S/M258A(M3)was identified by saturation mutagenesis and iterative combinatorial mutagenesis,which exhibited a 102-fold increase in the catalytic efficiency relative to that of wild-type enzyme and high diastereoselectivity(98:2 d.r.).Crystal structural analysis and molecular dynamics simulations provided some insights into the molecular basis for the improved activity of the mutant enzyme.The imine reductase identified in this study could accept chiral amino amides/esters as amino donors for the dynamic kinetic resolution reductive amination of racemicα-substituted aldehydo-esters,expanding the substrate scope of imine reductases in the dynamic kinetic resolution-reductive amination.Finally,IR104-M3 was successfully used for the preparation of Brivaracetam at gram scale.Using this mutant,various N-substituted amino amides/esters with two chiral centers were also synthesized with up to 99:1 d.r.and 96%yields and subsequently converted intoγ-andδ-lactams,providing an efficient protocol for the synthesis of these important compounds via enzymatic dynamic kinetic resolution-reductive amination from simple building blocks.
基金the financial support from the National Natural Science Foundation of China(NSFC,Nos.22171042,21831002,and 22193012)the Jilin Province Natural Science Foundation(No.20160520140JH)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Ten Thousand Talents Program for generous financial support。
文摘Catalytic Michael addition reaction represents a fundamental importance in organic synthetic chemistry.Whereas corresponding conversions toward intrinsically low reactive enamide remains an ongoing challenging.We herein report a copper-catalyzed conjugate addition of allenes toβ-substituted alkenyl amides,one of the most challenging Michael acceptors.The present method utilizes readily available allenes as the latent carbon-based nucleophiles and simple,commonβ-substituted alkenyl amides as starting materials,unlike previous methods that usually preinstall an activating group to improve the reactivity of amide or uses highly reactive stoichiometric quantities of organometallics.Hence,this approach shows good functional group compatibility and can be implemented under mild reaction conditions with excellent level of chemo-and regioselectivities.
基金supported by the National Natural Science Foundation of China(No.21372176)Tongji University 985 Phase Ⅲ funds+1 种基金Pujiang Project of Shanghai Science and Technology Commission(No.11 J1409800)the Program for Professor of Special Appointment(Eastern Scholar) at Shanghai Institutions of Higher Learning
文摘A highly efficient copper-catalyzed approach to form amide bonds from formamides and carboxylic acids was developed. This protocol shows broad substrate scopes and high yields in the presence of 1 mol% catalyst and 4.0 equiv, formamides.
文摘The development of economic and environmentally friendly extractants to recover cobalt metal is required due to the increasing demand for this metal.In this study,solvent extraction of Co（Ⅱ） from aqueous solution using a mixture of N,N＇-carbonyl difatty amides（CDFAs） synthesised from palm oil as the extractant was carried out.The effects of various parameters such as acid,contact time,extractant concentration,metal ion concentration and stripping agent and the separation of Co（Ⅱ） from other metal ions such as Fe（Ⅱ）,Ni（Ⅱ）,Zn（Ⅲ） and Cd（Ⅱ） were investigated.It was found that the extraction of Co（Ⅱ） into the organic phase involved the formation of 1：1 complexes.Co（Ⅱ） was successfully separated from commonly associated metal ions such as Fe（Ⅱ）,Ni（Ⅱ）,Zn（Ⅲ） and Cd（Ⅱ）.Co（Ⅱ） stripping from the loaded organic phase was studied in aqueous solution.These results are useful to recover Co（Ⅱ） from aqueous solution utilising（CDFAs） as an extractant.
基金The authors are grateful to agricultural com-prehensive development project of science and technology in Ningxia province(Research on Chinese wolfberry active substances and health products)STS project of Chinese Academy of Sciences for the financial support.
文摘Four new phenolic amides,4-O-methylgrossamide(1),(E)-2-(4,5-dihydroxy-2-{3-[(4-hydrox-yphenethyl)amino]-3-oxopropyl}-phenyl)-3-(4-hydroxy-3-methoxyphenyl)-N-(4-hydroxyphenethyl)acryl-amide(2),(Z)-lyciumamide C(3),(Z)-thoreliamide B(4),together with thirteen known phenolic amides were identified from the stem of Lycium barbarum.The structures of the new compounds were determined by spectroscopic methods.All compounds were evaluated for their anti-cancer activities against human glioma stem cell lines.
基金the National Natural Science Foundation of China(Nos.91644214,21677089,21876102)the Shenzhen Science and Technology Research and Development Funds(No.JCYJ20160510165106371)+2 种基金the Fundamental Research Funds of Shandong University(Nos.2016WLJH51,2017JC033)The China Postdoctoral Science Foundation funded project(Nos.2017M612277,2017T100493)The open foundation of state key laboratory of environmental criteria and risk assessment,Chinese Research Academy of Environmental Sciences(Nos.2016OFP09)。
文摘Amides,a series of significant atmospheric nitrogen-containing volatile organic compounds(VOCs),can participate in new particle formation(NPF)throught interacting with sulfuric acid(SA)and organic acids.In this study,we investigated the molecular interactions of formamide(FA),acetamide(AA),N-methylformamide(MF),propanamide(PA),Nmethylacetamide(MA),and N,N-dimethylformamide(DMF)with SA,acetic acid(HAC),propanoic acid(PAC),oxalic acid(OA),and malonic acid(MOA).Global minimum of clusters were obtained through the association of the artificial bee colony(ABC)algorithm and density functional theory(DFT)calculations.The conformational analysis,thermochemical analysis,frequency analysis,and topological analysis were conducted to determine the interactions of hydrogen-bonded molecular clusters.The heterodimers formed a hepta or octa membered ring through four different types of hydrogen bonds,and the strength of the bonds are ranked in the following order:SO-H···O>CO-H···O>N-H···O>C-H···O.We also evaluated the stability of the clusters and found that the stabilization effect of amides with SA is weaker than that of amines with SA but stronger than that of ammonia(NH 3)with SA in the dimer formation of nucleation process.Additionally,the nucleation capacity of SA with amides is greater than that of organic acids with amides.
文摘Lithium amides have been proved to be effective anionic initiators for the anionic polymerization of acrylonitrile to get high molecular weight polyacrylonitrile in this study. Polyacrylonitrile with weightaverage molecular weight ranging from 1.02 × 10~6 g/mol to 1.23 ×10~6 g/mol (M_w/M_n= 1.9-2.2) could be prepared utilizing lithium amides derived from diisopropylamine, diethylamine, hexamethyldisilazane,dicyclohexylamine, and 2,2,6,6-tetramethylpiperidine as initiators. The polymerization of acrylonitrile proceeded in a homogeneous manner in N,N-di methyl for mamide and insignificant contribution of side reactions was confirmed.
基金financially supported by the National Natural Science Foundation of China (Nos.31171877,31571991,21372132)the International Science & Technology Cooperation Program of China (No.2014DFR41030)
文摘A series of novel N-（3-furan-2-yl-l-phenyl-lH-pyrazol-5-yl） amides derivatives were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR and HRMS. All title compounds were evaluated for their herbicidal and antifungal activities. Preliminary bioassay results indicated that the title compounds showed good to moderate herbicidal activity at 1000 mg/L. Compound 6q presented the best activity against Digitaria sanguinalis （L） Scop., Amaranthus retroflexus L. and Arabidopsis thaliana with an inhibition degree of five. Compound 6d also showed an inhibition degree of five against D. sanguinalis. In addition, at 50 mg/L, most compounds exhibited good in vitro antifungal activity against Sclerotinia sclerotiorum, with compound 6c showing over 90% antifungal activity against S. sclerotiorum and Pellicularia sasakii.
基金This work was funded by the Southeast Asia Biodiversity Research Institute,Chinese Academy of Sciences(Y4ZK111B01)the Natural Science Foundation of Yunnan Province,China(2011FZ205)+2 种基金the International Partneship Program of Chinese Academy of Sciences(153631KYSB20160004)the Key Laboratory of Ethnomedicine(Minzu University of China)of Ministry of Education of China(KLEM-ZZ201806)the National Natural Science Foundation of China(31761143001&31161140345).
文摘One undescribedamide,pipermullesine A,twoundescribed isoquinoline alkaloids,pipermullesinesBand C,and six undescribed dipeptides,pipermullamides A–F,along with 28 known compounds,were isolated from the aerial parts of Piper mullesua.The structures of the undescribed compounds were elucidated based on the analysis of 1D and 2D NMR and MS data.Furthermore,the structures of pipermullesines A–Cwere confirmed by single crystal X-ray diffraction analysis.All isolates were evaluated for inhibitory activity against platelet aggregation induced by thrombin(IIa)or platelet-activating factor(PAF).(-)-Mangochinine,pellitorine,and(2E,4E)-N-isobutyl-2,4-dodecadienamide showed weak inhibitory activity against rabbit platelet aggregation induced by PAF,with IC_(50)values of 470.3μg/mL,614.9μg/mL,and 579.7μg/mL,respectively.
文摘Indium(III) triflate, a trivalent indium reagent, was shown to be a highly-efficient catalyst for the conversion of primary amides to the corresponding nitriles. The successful reactions required 5 mol% of indium(III) triflate, and toluene was proved to be the most suitable solvent. Various amides were subjected to this method, and each produced the corresponding nitriles in excellent yields.
基金The National Natural Science Foundation of China(Grant No.21002002)the Beijing Natural Science Foundation(Grant No.7162110)
文摘Based on the structure of compound B51（IC_（50） = 37.4 μM）, which was discovered as hit in a previous virtual screen, a series of methylisoxazole/isothiazole amide derivatives were designed and synthesized as BACE1 inhibitors. The methoxyphenylpyrimidone fragment of B51 was transformed into a methoxyphenylmethylisoxazole/isothiazole moiety to reduce the molecular weight while retaining the ability to fit into the S1＇ and S2＇ subpocket of BACE1 as predicted by docking studies. The effects of BACE1 inhibition and the structure-activity relationships were analyzed. Among all 20 designed compounds, 5t exhibited almost 10-fold improved potency（IC_（50） = 5.33 μM） compared to B51 in the BACE1 inhibition assay. Additionally, it has exhibited ＂rapid binding, slow dissociation＂ kinetics in SPR analysis, suggesting a longer inhibitory effect than B51. All acquired methylisoxazole/isothiazole derivatives were small in size and safe to normal cells, which allow them represent a novel scaffold for BACE1 inhibitor design.
文摘?β-Unsaturated amides with various substitution pattems at the carbon-carbon double And and nitrogen atom can be reduced to the corresponding saturated amides with high selectivity and yields with NaBH4/BiCl3 system.
基金financial support from the National Natural Science Foundation of China(No.21332007)the Program for Changjiang Scholars and Innovative Research Team in University(PCSIRT) of Ministry of Education+1 种基金the Fundamental Research Funds for the Central Universities(No.20720150044)the Natural Science Foundation of Fujian Province of China (No.2014J01062)
文摘Secondary amides are a class of highly stable compounds serving as versatile starting materials,intermediates and directing groups（amido groups） in organic synthesis.The direct deacylation of secondary amides to release amines is an important transformation in organic synthesis.Here,we report a protocol for the deacylation of secondary amides and isolation of amines.The method is based on the activation of amides with Tf_2O.followed by addition of organocerium reagents,and acidic work-up.The reaction proceeded under mild conditions and afforded the corresponding amines,isolated as their hydrochloride salts,in good yields.In combination with the C-H activation functionalization methodology,the method is applicable to the functionalization of aniline as well as conversion of carboxylic derivatives to functionalized ketones.
基金financial supports from the National Natural Science Foundation of China(Nos.21772035,22022204,22072167,21202206)Natural Science Foundation of Hunan Province(Nos.2021JJ40147)。
文摘α,β-Unsaturated primary amides are important intermediates and building blocks in organic synthesis.Herein,we report a ligand-free iron-catalyzed hydroaminocarbonylation of alkynes using NH_(4)HCO_(3)as the ammonia source,enabling the highly efficient and regioselective synthesis of linearα,β-unsaturated primary amides.Various aromatic and aliphatic alkynes are transformed into the desired linearα,β-unsaturated primary amides in good to excellent yields.Further studies show that using NH_(4)HCO_(3)as the ammonia source is key to obtain good yields and selectivity.The utility of this route is demonstrated with the synthesis of linearα,β-unsaturated amides including vanilloid receptor-1 antagonist TRPV-1.
基金supported by the Southeast Asia Biodiversity Research Institute,Chinese Academy of Sciences(2015CASEABRIRG001 and Y4ZK111B01)the open foundation of Key Laboratory of Ethnomedicine(Minzu University of China),Ministry of Education(KLEM-KF2018Z01)the International Partnership Program of Chinese Academy of Sciences(153631KYSB20160004).
文摘Two new amides(E)-N-cinnamoyl-2-methoxypiperidine(1)and(R)-1-(2-oxopyrrolidin-3-yl)-5,6-dihydropyridin-2(1H)-one(2),four new amide glucosides,retrofractosides A-D(3-6),and two new phenylpropanoid glucosides,retrofractosides E(7)and F(8),together with 24 known compounds(9-32)were isolated from the fruits of Piper retrofractum.The chemical structures of these new compounds were elucidated based on extensive spectroscopic analysis.All of these isolates(1-32)were evaluated for inhibitory activity against mouse platelet aggregation induced by the peptide AYPGKF-NH2.(E)-N-(Tetrahydro-2H-pyran-2-yl)cinnamamide(9)showed a weak inhibitory efect,with an inhibition ratio of 52.0%at a concentration of 150μM.
基金This project is financially supported by Hi-tech Research and Development Program(2003AA33g-030)the National Natural Science Foundation of China(Contract grant number:50143013).
文摘A novel aromatic diamine, 1, 2-dihydro-2-（4-aminophenyl）-4-[3-methoxy-4-（4-aminophenoxy）]-2, 3-phthalazin-l-one （OO-DA） containing aza heterocyclic structure was synthesized from the bisphenol-like monomer in two steps and used for preparing new aromatic polyamides with high inherent viscosity of 0.89-1.03 dL.g^-1. The structures of diamine and polymers obtained were confirmed by MS, PT-IR, WAXD and ^1H-NMR. The synthesized polymers exhibited high glass transition temperature in the range of 281-307℃ and good solubility in polar solvents.
