Decarboxylation with Carbon Monoxide: The Direct Conversion of Carboxylic Acids into Potent Acid Triflate Electrophiles

Abstract

We report a new strategy for the conversion of carboxylic acids into potent acid triflate electrophiles. The reaction involves oxidative carbonylation of carboxylic acids with I2 in the presence of AgOTf, and is postulated to proceed via acyl hypoiodites that react with CO to form acid triflates. Coupling this chemistry with subsequent trapping with arenes offers a mild, room temperature approach to generate ketones directly from broadly available carboxylic acids without the use of corrosive and reactive Lewis or Bronsted acid additives, and instead from compounds that are readily available, stable, and functional group compatible.

Fabrication of Black In2O3 with Dense Oxygen Vacancy through Dual Functional Carbon Doping for Enhancing Photothermal CO2 Hydrogenation

“…[ 4 ] Typically, high purity CO from CO 2 hydrogenation via reverse water gas shift (RWGS) reaction could be used as raw material for the Fischer–Tropsch synthesis. [ 5 ] producing carbonyl‐containing compounds, [ 6 ] acetamides, [ 7 ] triflate electrophiles, [ 8 ] and purifying nickel in Mond process. [ 9 ] In this way, photothermal catalytic CO 2 reduction technology can significantly reduce energy consumption and seems promising for carbon recycle, but the fabrication of high‐quality catalyst is not yet mature.…”

Denitrative Sulfonylation of Nitroarenes with Sodium Sulfinates

“…Spectroscopic data matched those reported in literature. 18 This article is protected by copyright. All rights reserved.…”

Nanocellulose as Convenient Reaction Media for the FeCl3 Mediated Mechanochemical Synthesis of 3-Acylchromones

“…19 A decarboxylative approach for the acylation of (hetero)arenes has been disclosed by Kinney and Arndtsen via direct conversion of carboxylic acids into acid triflate electrophiles using a synergy of CO, I 2 , and AgOTf. 20 In a seminal experiment in 2021, Chen and co-workers reported the acylation of azoles with carboxylic acids in the presence of various bulky phosphine ligands through the Pd/Cu cooperative catalysis. 21 During the same time, a photoredox acylation approach for the synthesis of γ-oxo-α-amino acid derivatives has also been reported which employed photoredox catalysis in combination with triphenylphosphine to generate acyl radicals from the readily available (hetero)aromatic and vinylic carboxylic acids.…”

“…Later, Fu et al reported a different strategy for the acylation of 2-phenylpyridines with aromatic acids using Pd­(OAc) 2 as the catalyst, and trifluoroacetic anhydride as the activating agent of the acids . A decarboxylative approach for the acylation of (hetero)­arenes has been disclosed by Kinney and Arndtsen via direct conversion of carboxylic acids into acid triflate electrophiles using a synergy of CO, I 2 , and AgOTf . In a seminal experiment in 2021, Chen and co-workers reported the acylation of azoles with carboxylic acids in the presence of various bulky phosphine ligands through the Pd/Cu cooperative catalysis .…”