Pd/C-Catalyzed Aminocarbonylation of Aryl Iodides via Oxidative C–N Bond Activation of Tertiary Amines to Tertiary Amides

Abstract

This work reports oxidative N-dealkylation/carbonylation of tertiary amines to tertiary amides by using molecular oxygen as a sole oxidant using a Pd/C catalyst. This protocol is free from ligands, additives, bases, and cocatalysts. Different tertiary amines as well as aryl iodides have been examined for this transformation, providing desired products in good to excellent yield.

Synthesis of Amido Esters and Amido Phosphonates through Carbonylation of Diazo Compounds Followed by Nucleophilic Addition Reaction

“…[7][8][9][10] Because of its importance, several synthetic methods have been developed to prepare different types of amides, most of which start from carbonyl compounds and amines. [14][15][16][17] These known methods, however, are not fully suitable to the synthesis of amido esters and amido phosphonates because of their low functional-group tolerance. [14][15][16][17] These known methods, however, are not fully suitable to the synthesis of amido esters and amido phosphonates because of their low functional-group tolerance.…”

“…[11][12][13] Widely used methods include: (i) carbonylation followed by amidation and (ii) the hydroamidation of alkynes and nitriles. [14][15][16][17] These known methods, however, are not fully suitable to the synthesis of amido esters and amido phosphonates because of their low functional-group tolerance. [11,15] Under certain reaction conditions, the Ritter reaction, the reaction of isonitriles and compounds with active methylene groups, and an amino carbonylation strategy can be employed for the synthesis of amido esters.…”

Palladium‐Catalyzed Aerobic Oxidative Carbonylation of C–H Bonds in Phenols for the Synthesis of p‐Hydroxybenzoates

“…Transition‐metal‐catalyzed carbonylation of aryl halides or pseudohalides, established in 1974 by Heck and co‐workers, has served as a most potent methodology for the synthesis of carboxylic acids and their derivatives. On the other hand, activation of inert C–H bonds is a very attractive but difficult goal in synthetic chemistry; however, with the correct selection of catalyst and substrate it can be achieved Even so, carbonylation of C–H bonds presents a great challenge and is an attractive field.…”

Solvent‐Switchable Regioselective Synthesis of Aurones and Flavones Using Palladium‐Supported Amine‐Functionalized Montmorillonite as a Heterogeneous Catalyst

“…With this goal and in continuation of our recent work on the development of heterogeneous catalysis and carbonylation reactions, herein we report the solvent‐switchable regioselective synthesis of flavones and aurones by the three‐component coupling reaction of 2‐iodophenols, terminal alkynes, and CO using Pd 0 APTES@K10 (APTES=(3‐aminopropyl)triethoxysilane) as a recyclable catalyst (Scheme ).…”