The synthesis and structures of two novel zwitterionic ruthenium triazolato complexes are reported. The treatment of the ruthenium azido complex [Ru]-N3 (1, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with an ex...The synthesis and structures of two novel zwitterionic ruthenium triazolato complexes are reported. The treatment of the ruthenium azido complex [Ru]-N3 (1, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with an excess of ethyl propiolate in CHCl3 or CH2Cl2 under ambient conditions for 15 days results in the formation of a mixture of the Z- and E-forms of N(1)-bound ruthenium 3-ethylacryl-4-carboxylate-3H-1,2,3-triazolato complexes [Ru]N3(CH=CHCO2Et)C2H(CO2) (Z-3) and (E-3) in a ratio of ca. 5:2. The structures of E-3 and Z-3 were confirmed by single-crystal X-ray diffraction analysis and fully characterized by 1H, 31P, 13C NMR and IR spectroscopy, mass spectrometry, and elemental analysis. The negatively charged carboxylate moieties of the zwitterionic ruthenium triazolato complexes Z-3 and Z-3 are highly nucleophilic and reactive toward a variety of electrophiles, making Z-3 and Z-3 potential starting materials for the development of biologically active 1,2,3-triazole derivatives.展开更多
A novel, convenient and efficient approach to the synthesis of pyrrole and imidazole derivatives via the reaction between primary amines, alkyl propiolates or isothiocyanate and oxalyl chloride is described. The metho...A novel, convenient and efficient approach to the synthesis of pyrrole and imidazole derivatives via the reaction between primary amines, alkyl propiolates or isothiocyanate and oxalyl chloride is described. The method offers several advantages including high yields of products and performing reaction under solvent-free conditions.展开更多
The addition of α-keto amides as a NH-acid to alkyl propiolates and dialkyl acetylenedicarboxylates in the presence of a catalytic amount of triphenylphosphine gives the corresponding substituted alkyl acrylates.
The addition of 2,4-dihydroxyaceto(and benzo)phenone to propiolic ester is catalyzed by triphenylphosphine or tert-butyl isocyanide to form O-vinyl aryl derivatives in fairly good yields.
The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and...The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and Au)catalysis has emerged as a synthetic strategy for a wide range of organic chemical reactions in past decades.In coinage-metal-catalyzed carboxylation,CO_(2)is adopted as a carboxylation reagent,while coinage-metal salts,complexes,and nanoparticles(NPs)serve as a Lewis acid catalyst to activate unsaturated chemicals,particularly alkynes.This mini-review focuses on the recent advances of coinage-metal-catalyzed carboxylation of terminal alkynes with CO_(2).Other respects,such as the role of bases,the influence of trace water,and solvent effects are also highlighted.展开更多
Stable derivatives of pyrroles were prepared using multicomponent reactions of dialkyl acetylenedicarboxylate, primary amine and propiolate in the presence of N-methylimidazole in water at room temperature in good yie...Stable derivatives of pyrroles were prepared using multicomponent reactions of dialkyl acetylenedicarboxylate, primary amine and propiolate in the presence of N-methylimidazole in water at room temperature in good yields.展开更多
Methyl propiolate, formaldehyde, and various acyclic amines were assembled in one-pot into a series of 1,5-diaza-2,6-cyclooctadiene-3,7-dicarboxylates in moderate to good yields. This multiple-component reaction benef...Methyl propiolate, formaldehyde, and various acyclic amines were assembled in one-pot into a series of 1,5-diaza-2,6-cyclooctadiene-3,7-dicarboxylates in moderate to good yields. This multiple-component reaction benefits from operational simplicity as well as good material economy.展开更多
A three-component condensation was applied for the preparation of cyclopentadiene derivatives through the reaction of primary amines,alkyl propiolate and dialkyl acetylenedicarboxylate in the presence of catalytic amo...A three-component condensation was applied for the preparation of cyclopentadiene derivatives through the reaction of primary amines,alkyl propiolate and dialkyl acetylenedicarboxylate in the presence of catalytic amount of ZnO-nanorods(Zn-NR) under solvent-free conditions at 50 ℃.The method has proved to be synthetically green,simple,and effective with high atom economy and yield.The catalyst also revealed significant reusability.Moreover,the antioxidant activity and free radical scavenging capacity of the newly synthesized derivatives 4a,4b,4c,and 4d was screened using free radical scavenging 2,2-diphenyl-1-picrylhydrazyl(DPPH) and ferric reducing antioxidant power(FRAP)assays and compared with hydroxytoluene(BHT) and tert-butylhydroquinone(TBHQ).These compounds do not exhibit good DPPH radical scavenging,but they have a desirable FRAP.展开更多
A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of pr...A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of prefabricated arylselenation reagent and address the facile over-selention issues,but also enrich the chemistry of selenium powder.Importantly,this reaction could be extended to pyrrole,and the practical utility of this transformation has been demonstrated in gram-scale synthesis and late-stage indolylselenation of Clofibrate-derived propiolic acid.展开更多
文摘The synthesis and structures of two novel zwitterionic ruthenium triazolato complexes are reported. The treatment of the ruthenium azido complex [Ru]-N3 (1, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with an excess of ethyl propiolate in CHCl3 or CH2Cl2 under ambient conditions for 15 days results in the formation of a mixture of the Z- and E-forms of N(1)-bound ruthenium 3-ethylacryl-4-carboxylate-3H-1,2,3-triazolato complexes [Ru]N3(CH=CHCO2Et)C2H(CO2) (Z-3) and (E-3) in a ratio of ca. 5:2. The structures of E-3 and Z-3 were confirmed by single-crystal X-ray diffraction analysis and fully characterized by 1H, 31P, 13C NMR and IR spectroscopy, mass spectrometry, and elemental analysis. The negatively charged carboxylate moieties of the zwitterionic ruthenium triazolato complexes Z-3 and Z-3 are highly nucleophilic and reactive toward a variety of electrophiles, making Z-3 and Z-3 potential starting materials for the development of biologically active 1,2,3-triazole derivatives.
文摘A novel, convenient and efficient approach to the synthesis of pyrrole and imidazole derivatives via the reaction between primary amines, alkyl propiolates or isothiocyanate and oxalyl chloride is described. The method offers several advantages including high yields of products and performing reaction under solvent-free conditions.
文摘The addition of α-keto amides as a NH-acid to alkyl propiolates and dialkyl acetylenedicarboxylates in the presence of a catalytic amount of triphenylphosphine gives the corresponding substituted alkyl acrylates.
文摘The addition of 2,4-dihydroxyaceto(and benzo)phenone to propiolic ester is catalyzed by triphenylphosphine or tert-butyl isocyanide to form O-vinyl aryl derivatives in fairly good yields.
文摘The conversion of inexpensive,available C1 feedstock of carbon dioxide(CO_(2))into value-added fine chemicals via homogeneous or heterogeneous catalysis has attracted great recent interest.Coinagemetal-based(Cu,Ag,and Au)catalysis has emerged as a synthetic strategy for a wide range of organic chemical reactions in past decades.In coinage-metal-catalyzed carboxylation,CO_(2)is adopted as a carboxylation reagent,while coinage-metal salts,complexes,and nanoparticles(NPs)serve as a Lewis acid catalyst to activate unsaturated chemicals,particularly alkynes.This mini-review focuses on the recent advances of coinage-metal-catalyzed carboxylation of terminal alkynes with CO_(2).Other respects,such as the role of bases,the influence of trace water,and solvent effects are also highlighted.
文摘Stable derivatives of pyrroles were prepared using multicomponent reactions of dialkyl acetylenedicarboxylate, primary amine and propiolate in the presence of N-methylimidazole in water at room temperature in good yields.
文摘Methyl propiolate, formaldehyde, and various acyclic amines were assembled in one-pot into a series of 1,5-diaza-2,6-cyclooctadiene-3,7-dicarboxylates in moderate to good yields. This multiple-component reaction benefits from operational simplicity as well as good material economy.
基金the support of the Research Council of Iran University of Science and Technology, Tehran, Iran
文摘A three-component condensation was applied for the preparation of cyclopentadiene derivatives through the reaction of primary amines,alkyl propiolate and dialkyl acetylenedicarboxylate in the presence of catalytic amount of ZnO-nanorods(Zn-NR) under solvent-free conditions at 50 ℃.The method has proved to be synthetically green,simple,and effective with high atom economy and yield.The catalyst also revealed significant reusability.Moreover,the antioxidant activity and free radical scavenging capacity of the newly synthesized derivatives 4a,4b,4c,and 4d was screened using free radical scavenging 2,2-diphenyl-1-picrylhydrazyl(DPPH) and ferric reducing antioxidant power(FRAP)assays and compared with hydroxytoluene(BHT) and tert-butylhydroquinone(TBHQ).These compounds do not exhibit good DPPH radical scavenging,but they have a desirable FRAP.
基金Financial support from the National Natural Science Foundation of China(Nos.81803484,21602158)Zhejiang Provincial Natural Science Foundation(No.LY19B020011)Public Welfare Science and Technology Project of Wenzhou(Nos.Y20190132,Y20180233)are greatly appreciated.
文摘A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of prefabricated arylselenation reagent and address the facile over-selention issues,but also enrich the chemistry of selenium powder.Importantly,this reaction could be extended to pyrrole,and the practical utility of this transformation has been demonstrated in gram-scale synthesis and late-stage indolylselenation of Clofibrate-derived propiolic acid.