Pd-Catalyzed N-Formylation of Amines with N,N-Dimethylformamide

Abstract

A highly efficient protocol for the transamidation of N,N-dimethylformamide (DMF) and amines has been developed, utilizing a catalytic amount Pd(OAc)2. This methodology has a broad substrate scope for aliphatic, aromatic, and heterocyclic amines. And this process is simple and easily performed without solvent and co-catalyst.

A Journey from June 2018 to October 2021 with N,N-Dimethylformamide and N,N-Dimethylacetamide as Reactants

“…Such a pathway contrasts with the proposal of Gong and co-workers who assumed the direct amine addition to the DMF/Co II complex [109] as above alleged under Fe III catalysis [92]. No mechanism was indicated by L. Zhang's team for the Pd-catalyzed reaction [108]; the yield decreased in the absence of NEt3 (Scheme 33j), leading us to suspect a pathway similar to that mediated by Cu II .…”

“…Heating was required for the amidation of arylamines mediated with graphene oxide under neat conditions (Scheme 34f) [106]. N-Amidation of aryl and aliphatic amines arose in high yields at 80-150 °C under CuCl2 (Scheme 33i) [107] or PdCl2 catalysis (Scheme 33j) [108] while Co(OAc)2 as catalyst was efficient only from aliphatic amines (Scheme 33k) [109]. The Cu-catalyzed reaction was carried out in the presence of 1,2,4-triazole.…”

Metal-Free N-Formylation of Amines Using Carbohydrates as C1 Synthon via C–C Bond Cleavage

“…In this regard, in order to avoid the conventional toxic reagents as used in the past, various formylation methods using different C1 synthons have been developed and reported in the literature. A list of reagents and solvents those act as C1 synthons include carbon monoxide (CO), 51,52 carbon dioxide (CO 2 ), [53][54][55][56][57][58][59] paraformaldehyde, 60,61 trialkyl orthoformate [62][63][64] methanol (MeOH), [65][66][67][68][69][70] dimethylformamide (DMF), [71][72][73][74][75][76] ethers, [77][78][79] glycolaldehyde, 80 glyceraldehyde, 81 glycolic acid, 81 1,3-dihydroxyacetone 81 and these incorporate CHO, CN, CH, CH 2 , and CH 3 in organic molecules. Among above mentioned reagents DMF, and MeOH are the most significant due to their cost-effectiveness, low toxicity, and easy availability.…”