Decarboxylative Arylation Research Articles

Nickel-Catalyzed Decarboxylative Arylation of Azoles with Perfluoro- and Nitrobenzoates.

This manuscript describes a Ni-catalyzed method for the direct arylation of azoles using benzoates. Perfluorophenyl and 2-nitrobenzoates participate in these reactions to afford the corresponding products in modest to good yields. The efficiency of the arylations with perfluorobenzoates is highly dependent on both the degree and position of fluorine atoms in the benzoates.

Nickel‐Catalyzed Decarboxylative Arylation of Heteroarenes through sp2 C–H Functionalization

AbstractThe direct decarboxylative arylation of hetereoarenes with benzoic acids through a nickel‐catalyzed sp2 C–H functionalization process was developed. This process provides the first examples of decarboxylative cross‐coupling reactions with aromatic acids through nickel catalysis and tolerates a variety of functional groups. Moreover, this method provides efficient access to 2‐aryl‐substituted azoles, an important structural unit in natural products, medicinal compounds, and functional materials.

ChemInform Abstract: Decarboxylative Arylation of α‐Amino Acids via Photoredox Catalysis: A One‐Step Conversion of Biomass to Drug Pharmacophore.

The direct decarboxylative arylation of α-amino acids has been achieved via visible light-mediated photoredox catalysis. This method offers rapid entry to prevalent benzylic amine architectures from an abundant biomass, specifically α-amino acid precursors. Significant substrate scope is observed with respect to both the amino acid and arene components.

Palladium‐Catalyzed Decarboxylative C–H Bond Arylation of Furans

AbstractA Pd/PCy3/Ag2CO3 (Cy = cyclohexyl) catalytic system was found to promote decarboxylative arylation through the combination of decarboxylation and C–H bond functionalization. This protocol features a good substrate scope of aromatic carboxylic acids as well as a broad range of functional groups and provides the products in high yields.

Synthesis of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) and its higher homologs through palladium-catalyzed intramolecular decarboxylative arylation

We report herein an effective method for the construction of 4- and 7-ring benzo-fused thieno[3,2-b]thiophenes, involving palladium-catalyzed intramolecular decarboxylative arylation as the key step.

ChemInform Abstract: Copper‐Catalyzed Oxidative Decarboxylative Arylation of Benzothiazoles with Phenylacetic Acids and α‐Hydroxyphenylacetic Acids with O2 as the Sole Oxidant.

A Cu(II)-catalyzed oxidative decarboxylative synthesis of 2-aryl benzothiazole from phenylacetic acids and α-hydroxyphenylacetic acids has been developed. This reaction proceeds via Cu(II)-catalyze...

Decarboxylative Arylation of α-Amino Acids via Photoredox Catalysis: A One-Step Conversion of Biomass to Drug Pharmacophore

The direct decarboxylative arylation of α-amino acids has been achieved via visible light-mediated photoredox catalysis. This method offers rapid entry to prevalent benzylic amine architectures from an abundant biomass, specifically α-amino acid precursors. Significant substrate scope is observed with respect to both the amino acid and arene components.

Pd‐Catalyzed Decarboxylative Cross‐Coupling of 2‐Carboxyazine N‐Oxides with Various (Hetero)aryl Halides

Decarboxylative cross-coupling reactions of substituted 2-carboxyazine N-oxides, with a variety of (hetero)aryl halides, by bimetallic Pd(0)/Cu(I) and Pd(0)/Ag(I) catalysis are reported. Two possible pathways, a conventional bimetallic-catalyzed decarboxylative arylation, as well as a protodecarboxylative/direct C-H arylation sequence have been considered. These methods provide the first general decarboxylative arylation methodology for the 2-carboxyazine series.

Cover Picture: Total Synthesis of Resveratrol-Based Natural Products Using a Palladium-Catalyzed Decarboxylative Arylation and an Oxidative Heck Reaction (Angew. Chem. Int. Ed. 9/2014)

Cover Picture: Total Synthesis of Resveratrol-Based Natural Products Using a Palladium-Catalyzed Decarboxylative Arylation and an Oxidative Heck Reaction (Angew. Chem. Int. Ed. 9/2014)

Total Synthesis of Resveratrol‐Based Natural Products Using a Palladium‐Catalyzed Decarboxylative Arylation and an Oxidative Heck Reaction

Controlled access to resveratrol-based natural products is offered by a novel, modular concept. A common building block readily available on a large scale serves as the starting material for the introduction of structurally important aryl groups by a Pd-catalyzed decarboxylative arylation and an oxidative Heck reaction with good yields and high stereoselectivity. The modular approach is convincingly documented by the successful synthesis of three racemic resveratrol-based natural products (quadrangularin A, ampelopsin D, and pallidol).

Copper-Catalyzed Oxidative Decarboxylative Arylation of Benzothiazoles with Phenylacetic Acids and α-Hydroxyphenylacetic Acids with O2 as the Sole Oxidant

A Cu(II)-catalyzed oxidative decarboxylative synthesis of 2-aryl benzothiazole from phenylacetic acids and α-hydroxyphenylacetic acids has been developed. This reaction proceeds via Cu(II)-catalyzed decarboxylation, C-H bond oxidation, ring-opening, and condensation steps in a one-pot protocol with dioxygen as the sole terminal oxidant. Various functional groups were tolerated under standard conditions, and isolated yields were as high as 95%.

Synthesis of 3,4‐Disubstituted Quinolin‐2‐(1H)‐ones via Palladium‐Catalyzed Decarboxylative Arylation Reactions

AbstractThe Pd‐catalyzed decarboxylative cross‐coupling reaction of 4‐substituted quinolin‐2(1H)‐one‐3‐carboxylic acids with (hetero)aryl halides is described. With palladium(II) bromide and triphenylarsine ligand as the catalyst system, a variety of 4‐substituted 3‐(hetero)aryl quinolin‐2(1 H)‐ones and related heterocycles, such as 4‐substituted 3‐arylcoumarins can be prepared in good to excellent yields.

Palladium-Catalyzed Decarboxylative Arylation of Benzoylacrylic Acids toward the Synthesis of Chalcones

It has been found that readily available 3-benzoylacrylic acids undergo palladium-catalyzed decarboxylative arylation with arylboronic acids in the presence of a copper salt oxidant to produce chalcone derivatives. The decarboxylative arylation could also be achieved using aryl halides as the alternative aryl source to expand the applicable scope.

Decarboxylative benzylation and arylation of nitriles

Decarboxylative benzylation of nitriles is achieved via coupling of metallated nitriles with Pd-π-benzyl complexes that are generated in situ from cyanoacetic benzyl esters. In addition, decarboxylative couplings of α,α-disubstituted 2-methylfuranyl cyanoacetates can lead to either decarboxylative arylation or benzylation depending on the reaction conditions.

ChemInform Abstract: Stereospecific Palladium‐Catalyzed Decarboxylative C(sp3)—C(sp2) Coupling of 2,5‐Cyclohexadiene‐1‐carboxylic Acid Derivatives with Aryl Iodides.

AbstractPalladium‐catalyzed decarboxylative arylation of 2,5‐cyclohexadiene‐1‐carboxylic acids (I) with aryl iodides proceeds smoothly to give 5‐arylated 1,3‐cyclohexadienes (III) in good yields.

Stereospecific Palladium‐Catalyzed Decarboxylative C(sp3)C(sp2) Coupling of 2,5‐Cyclohexadiene‐1‐carboxylic Acid Derivatives with Aryl Iodides

Palladium-catalyzed decarboxylative arylation of 2,5-cyclohexadiene-1-carboxylic acids (I) with aryl iodides proceeds smoothly to give 5-arylated 1,3-cyclohexadienes (III) in good yields.

Palladium-Catalyzed Decarboxylative Arylation of Potassium Cyanoacetate: Synthesis of α-Diaryl Nitriles from Aryl Halides

A palladium-catalyzed decarboxylative coupling of potassium cyanoacetate with aryl bromides and chlorides is described. The reaction conditions feature the absence of additional strong inorganic bases and provide ester functional group tolerance. With Pd(dba)(2) and XPhos ligand as the catalyst system, α-diaryl nitriles can be obtained in good yields.

ChemInform Abstract: Pd‐Catalyzed Decarboxylative Arylation of Thiazole, Benzoxazole, and Polyfluorobenzene with Substituted Benzoic Acids.

AbstractThe process allows the preparation of the target compounds with high chemo‐ and regioselectivities.

Pd-Catalyzed Decarboxylative Arylation of Thiazole, Benzoxazole, and Polyfluorobenzene with Substituted Benzoic Acids

A Pd-catalyzed decarboxylative coupling of thiazoles and benzoxazole with various substituted benzoic acids is developed. The reaction is compatible with both electron-rich and electron-poor benzoic acids. It can also be extended to the synthesis of polyfluoro-substituted biaryls using polyfluorobenzenes as the starting materials.

Palladium-catalyzed intramolecular decarboxylative allylic arylation of α-aryl-γ-methylidene-δ-valerolactones

A palladium-catalyzed intramolecular decarboxylative cyclization of alpha-aryl-gamma-methylidene-delta-valerolactones, followed by olefin isomerization, has been developed to give fused polycyclic aromatic compounds under mild conditions. The process described here can be regarded as a formal decarboxylative allylic arylation without using a pre-formed organometallic nucleophile. The reaction can be conducted on a gram scale and the products thus obtained are further derivatized with ease.