Palladium‐Catalyzed Aminocarbonylation Reaction to Access 1,2,3‐Triazole‐5‐carboxamides Using Dimethyl Carbonate as Sustainable Solvent

Abstract

A simple and direct palladium‐catalyzed aminocarbonylation of 5‐iodo‐1,2,3‐triazoles backbone for the incorporation of an amide functional group is presented. The approach is based on the palladium catalyzed carbonylative coupling reaction of iodo‐triazole with different amines employing formic acid and sulfuric acid as CO source (Morgan's reaction) to provide the 1,2,3‐triazole‐5‐carboxamides in good to excellent yields. The important features of this methodology include short reaction time, high yields, the use of dimethyl carbonate as a sustainable solvent, and the use of efficient alternative source of carbon monoxide, avoiding pressurized cylinder. The methodology described herein for the synthesis of 1,4,5‐trisubstituted 1,2,3‐triazole‐5‐carboxamides, can offers an alternative path for functionalization of other heterocycles.

A recent overview on the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles

“…In almost all cases, the desired triazole compounds were formed in good to high yield. The short reaction time, high yield, the use of dimethyl carbonate as a sustainable solvent, the use of an efficient alternative source of carbon monoxide, and avoiding a pressurized cylinder are some benefits of this protocol ( Scheme 35 ) [ 59 ].…”

“…Then, the intermediate 122 is obtained via a nucleophilic attack of amine 118 . Finally, a reductive elimination occurs in the presence of base to achieve the desired product 119 ( Scheme 36 ) [ 59 ].…”

5-Iodo-1H-1,2,3-triazoles as Versatile Building Blocks

“…In 2019, Schwab and co-workers reported the aminocarbonylation of 5-iodotriazoles using an alternative route for CO generation. 120 They used a two-chamber reaction vessel and generated CO ex situ from formic and sulfuric acid in one chamber, and this was then introduced into the second chamber for the Pd(PPh 3 ) 4 -catalyzed aminocarbonylation in dimethyl carbonate. This method was very efficient for the synthesis of a small library of triazole-5-carboxamides that generally possessed N-alkyl groups with various substituents within the alkyl chain.…”

Methyl 3-[(1-benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)formamido]propanoate: crystal structure, Hirshfeld surface analysis and computational chemistry

“…The title 1,2,3-triazole-5-carboxamide derivative, (I), was recently prepared and characterized from a palladium-catalysed aminocarbonylation reaction with the use of dimethyl carbonate as a sustainable solvent (de Albuquerque et al, 2019). The motivation for preparing such molecules rests with the known pharmacological activity of these and related 1,2,3triazole derivatives (Bonandi et al, 2017).…”

“…Compound (I) was prepared as described in the literature (de Albuquerque et al, 2019). The crystals were obtained by the slow evaporation from an ethanol solution of (I).…”