DMF·HCl as a versatile and straightforwardN- andO-formylating agent

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.…”

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

“…Martínez-Pascual and co-workers, who performed the formylation of anilines and secondary aliphatic amines using the beforehand prepared DMF . HCl complex, reported a domino reaction leading to 4-arylpiperazine-1-carbaldehydes from anilines, bis(2-chloroethyl)amine hydrochloride, and DMF (Scheme 34d) [103].Camphor sulfonic acid was the optimum carboxylic acid for N-formylation of 2-aminophenols at 100 • C (Scheme 34e) [104]. In contrast, Lewis acids such as tert-butyldimethylsilyl triflate promoted the room temperature formylation of primary or secondary aliphatic amines and anilines (Scheme 33h) [105].…”

“…amines using the beforehand prepared DMF . HCl complex, reported a domino reaction leading to 4-arylpiperazine-1-carbaldehydes from anilines, bis(2-chloroethyl)amine hydrochloride, and DMF (Scheme 34d) [103]. Camphor sulfonic acid was the optimum carboxylic acid for N-formylation of 2-aminophenols at 100 °C (Scheme 34e) [104].…”