Alkynyl Carboxylic Acids Research Articles

Copper‐Catalyzed Synthesis of Amino‐Substituted Polycyclic Aromatic Hydrocarbons by the Sequential Reaction between Aryl Alkynyl Carboxylic Acids and Amines

AbstractAmino‐substituted polycyclic aromatic hydrocarbons were obtained by the reaction between aryl alkynyl carboxylic acids and amines in the presence of a copper catalyst. The hydrocarbons were obtained in good yield without the need to isolate the 1,4‐diaryl‐1,3‐butadiyne intermediate. The best result was obtained using a combination of CuCl and Cu(OTf)2, and the reactions of cyclic and acyclic secondary amines afforded the desired products.

ChemInform Abstract: Palladium‐Catalyzed Oxidative Aminocarbonylation by Decarboxylative Coupling: Synthesis of Alkynyl Amides.

AbstractPalladium‐catalyzed aminocarbonylation for the synthesis of alkynyl amides from the coupling reactions of alkynyl carboxylic acids, amines, and carbon monoxide is reported.

Copper‐catalyzed One‐Pot Synthesis of Isoindolinones from 2‐Chlorobenzoic Acid, Aryl Alkynyl Carboxylic Acid, and Ammonium Acetate

Copper‐catalyzed One‐Pot Synthesis of Isoindolinones from 2‐Chlorobenzoic Acid, Aryl Alkynyl Carboxylic Acid, and Ammonium Acetate

ChemInform Abstract: Copper‐Catalyzed Ring Expansion of 2‐Aminobenzothiazoles with Alkynyl Carboxylic Acids to 1,4‐Benzothiazines.

AbstractA one‐pot synthesis of the title compounds (III) is presented via decarboxylative coupling, nucleophilic ring‐opening reaction, and an intramolecular hydroamination process.

Continuous flow reactions in water for the synthesis of propargylamines via a metal-free decarboxylative coupling reaction

A range of propargylamines was synthesized via the metal-free decarboxylative coupling of alkynyl carboxylic acids with amines and paraformaldehyde in water, using a continuous flow reaction system. Aryl- and alkyl-substituted propiolic acids were found to react with secondary amines in the presence of paraformaldehyde, at 140°C in water to give the desired propargylamines in good yield.

Copper-catalyzed direct synthesis of furans and thiophenes via decarboxylative coupling of alkynyl carboxylic acids with H2O or Na2S

2,5-Diaryl-substituted furans were synthesized from the copper-catalyzed decarboxylative coupling of aryl-substituted aryl propiolic acids in the presence of H2O. The homocoupling of alkynyl carboxylic acids provided 1,4-diaryldiynes, which then reacted with H2O to give the desired furans through cyclization. Addition of the copper catalyst was critical, and the addition of a ligand increased the yield of products in both the homocoupling and cyclization reactions. In addition, thiophenes could be obtained when the reaction was conducted in the presence of Na2S.

Decarboxylative Alkynyl Termination of Palladium-Catalyzed Catellani Reaction: A Facile Synthesis of α-Alkynyl Anilines via Ortho C-H Amination and Alkynylation.

A palladium-catalyzed synthesis of α-alkynyl anilines is reported. The reaction proceeds via Catellani ortho C-H amination followed by decarboxylative alkynylative amination. Different terminal alkyne precursors were screened, and it was found that alkynyl carboxylic acids were superior over other alkynes, which led to operationally simple reaction conditions (no gradual addition of alkynes) and broad substrate scope. The reactivity of three different components matched well; as a result, relatively higher reaction temperature could be used, greatly shortening the reaction time to 4 h from the previously reported 144 h.

ChemInform Abstract: Copper‐Catalyzed Selective Synthesis of Isoindolin‐1‐ones and Isoquinolin‐1‐ones from the Three‐Component Coupling of 2‐Halobenzoic Acid, Alkynylcarboxylic Acid and Ammonium Acetate.

AbstractAn efficient one‐pot synthesis of isoindolin‐1‐ones is described starting from 2‐iodobenzoic acid and arylalkynylcarboxylic acid or 2‐propinoic acid in the presence of ammonium acetate [cf.

β-ketophosphonate formation via aerobic oxyphosphorylation of alkynes or alkynyl carboxylic acids with H-phosphonates.

A synergistic Cu/Fe-catalyzed aerobic oxyphosphorylation of alkynes or alkynyl carboxylic acids with H-phosphonate is disclosed. The useful β-ketophosphonate products were obtained in good yields under oxygen atmosphere in a novel way. This reaction exhibits a wide substrate scope, and the mechanistic experiments indicate that a radical mechanism forms both C-P and C═O bonds simultaneously. This mechanism contrasts existing aerobic difunctionalization of alkynes.

Palladium‐Catalyzed Oxidative Aminocarbonylation by Decarboxylative Coupling: Synthesis of Alkynyl Amides

AbstractAlkynyl amides were synthesized from a palladium‐catalyzed coupling reaction of alkynyl carboxylic acids and amines under carbon monoxide. The reaction was conducted with palladium(II) acetate (5 mol‐%) and silver(I) oxide (1.0 equiv.) in acetonitrile at 80 °C for 1 h. This method provides good to moderate product yields and good functional group tolerance towards ketone, ester, and nitrile groups.

ChemInform Abstract: Copper(I)‐Catalyzed Decarboxylative Coupling of Propiolic Acids with Secondary Amines and Aldehydes.

An efficient microwave-assisted synthesis of tertiary propargylamines has been developed by copper(I)-catalyzed decarboxylative A3-coupling reaction of an alkynylcarboxylic acid with a secondary amine and an aldehyde. A wide range of diversely substituted propargylamines could be synthesized in high yields. The optimal reaction conditions are also effective for 3-alkylpropiolic acids and for terminal propiolic acid.

ChemInform Abstract: Copper‐Catalyzed Decarboxylative Coupling Reactions for the Synthesis of Propargyl Amines.

AbstractA facile protocol for the synthesis of a wide range of propargylamines from alkynyl carboxylic acids, aldehydes, and secondary amines is developed.

ChemInform Abstract: Thiosemicarbazone Salicylaldiminato Palladium(II)‐Catalyzed Alkynylation Couplings Between Arylboronic Acids and Alkynes or Alkynyl Carboxylic Acids.

AbstractTridentate Pd(II) salicylaldiminato‐thiosemicarbazone complexes can efficiently catalyze the alkynylation couplings of a variety of arylboronic acids with alkynes or alkynyl carboxylic acids under mild conditions.

Highly selective copper-catalyzed trifunctionalization of alkynyl carboxylic acids: an efficient route to bis-deuterated β-borylated α,β-styrene.

A copper-catalyzed highly efficient protocol for the synthesis of bis-deuterated β-borylated α,β-styrene derivatives, which can be further transformed to practical isotopically labeled compounds, has been developed. Alkynyl carboxylic acids are employed as alkyne synthons yet demonstrate a sharp discrepancy in reactivity and selectivity compared to terminal alkynes. Meanwhile, this reaction offers a novel and efficient strategy for highly selective trifunctionalization of the carbon-carbon triple bond at ambient temperature.

Copper-catalyzed ring expansion of 2-aminobenzothiazoles with alkynyl carboxylic acids to 1,4-benzothiazines

A new ring expansion of 2-aminobenzothiazoles with alkynyl carboxylic acids was developed, which allows for one-pot synthesis of 1,4-benzothiazines in moderate to excellent yields. The cascade reaction was achieved through decarboxylative coupling, nucleophilic ring-opening reaction and intramolecular hydroamination process.

Pd-catalyzed decarboxylative allylic coupling of acetates of Baylis–Hillman alcohols with propiolic acids: a highly regio- and stereoselective synthesis of 1,5-diarylpent-1-en-4-yne derivatives

Pd-catalyzed decarboxylative allylic coupling of acetates of Baylis–Hillman alcohols with alkynyl carboxylic acids leading to the formation of 1,5-diarylpent-1-en-4-ynes in a highly regio- and stereoselective manner has been developed.

ChemInform Abstract: Palladium‐Catalyzed Decarboxylative Trifluoroethylation of Aryl Alkynyl Carboxylic Acids.

A trifluoroethylation of alkynes through a palladium-catalyzed decarboxylative coupling reaction was developed. When alkynyl carboxylic acids and ICH2CF3 were allowed to react with [Pd(η3-allyl)Cl]2/XantPhos and Cs2CO3 in N,N-dimethylformamide (DMF) at 80 °C for 1 h, the desired products were formed in good yields. This catalytic system showed high functional group tolerance.

Copper‐Catalyzed Selective Synthesis of Isoindolin‐1‐ones and Isoquinolin‐1‐ones from the Three‐Component Coupling of 2‐Halobenzoic Acid, Alkynylcarboxylic Acid and Ammonium Acetate

AbstractIsoindolin‐1‐ones and isoquinolin‐1‐ones were selectively synthesized from the reaction of 2‐halobenzoic acid, arylalkynylcarboxylic acid and ammonium acetate (NH4OAc) in the presence of cesium carbonate (Cs2CO3) and a copper catalyst. Conducting the reaction under one‐pot conditions provided isoindolin‐1‐ones in good yields. Changing the addition sequence of ammonium acetate after all reagents had reacted at 120 °C for 6 h selectively produced isoquinolin‐1‐ones. A variety of arylalkynylcarboxylic acids produced the corresponding isoindolin‐1‐ones and isoquinolin‐1‐ones in good yields.magnified image

Copper(I)‐Catalyzed Decarboxylative Coupling of Propiolic Acids with Secondary Amines and Aldehydes

AbstractAn efficient microwave‐assisted synthesis of tertiary propargylamines has been developed by copper(I)‐catalyzed decarboxylative A3‐coupling reaction of an alkynylcarboxylic acid with a secondary amine and an aldehyde. A wide range of diversely substituted propargylamines could be synthesized in high yields. The optimal reaction conditions are also effective for 3‐alkylpropiolic acids and for terminal propiolic acid.

Copper-catalyzed decarboxylative coupling reactions for the synthesis of propargyl amines

When aryl alkynyl carboxylic acids were allowed to react with amines and aldehydes in CH3CN at 80°C in the presence of 10mol% CuI, the desired propargyl amines were formed in good yields. This coupling reaction demonstrated to work across a broad range of reagents including functionalized aryl alkynyl carboxylic acids, aliphatic and aromatic aldehydes, and cyclic and acyclic amines.