Synthesis, Characterization and Crystal Structures of Zwitterionic Triazolato Complexes by Reaction of a Ruthenium Azido Complex with Excess Ethyl Propiolate

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.

Solvent-free synthesis of substituted five membered heterocycles: One-pot reaction of primary amine and alkyl propiolate or isothiocyanate in the presence of oxalyl chloride

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.

An efficient synthesis of substituted alkyl acrylates using α-keto amides

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.

An efficient chemoselective synthesis of O-vinylaryl systems using acetylenic esters and dihydroxybenzenes in the presence of triphenylphosphine or alkyl isocyanides

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.

Recent advances in catalytic conversion of carbon dioxide to propiolic acids over coinage-metal-based catalysts

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.

Synthesis of highly functionalized pyrroles from primary amines and activated acetylenes in water

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.

One-pot Synthesis of 1,5-Diaza-2,6-cyclooctadiene-3,7-dicarboxylates Through a Multiple-component Reaction

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.

Synthesis,characterization and antioxidant activities of highly functionahzed cyclopentadienes catalyzed by ZnO-nanorod as economic and efficient heterogeneous nano catalyst

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.

Copper-catalyzed decarboxylative Se insertion coupling of indoles and propiolic acids

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.