N,N-Dimethylformamide (DMF) is a widely used polar aprotic solvent suitable for many types of reactions under a variety of conditions. Under certain conditions, DMF is also a valuable reagent and starting material for several synthetic transformations. For example, it can be used as a ligand in the preparation of metallic complexes, as a dehydrating agent, and as a formylating agent that can react with reactive nucleophilic agents. It is also known that amines can undergo N-formylation with DMF in the presence of certain additives or at high temperatures and long reaction times. Notably, some reactions of amines with DMF used as solvent are not very efficient and proceed with low yields. Due to the limited reactivity of DMF, the possibility of an efficient direct N-formylation of amines with DMF in the absence of any additive or catalyst has not been considered. Herein, we report efficient conditions, a likely novel mechanism, as well as the scope and limitation of the direct N-formylation of amines using DMF. In addition to providing a simple, scalable and inexpensive amine formylation process, these findings are helpful for recognizing the reaction conditions that can facilitate direct N-formylation of amines with DMF, so that those conditions can be considered when using DMF as a solvent.

Direct N-formylation of amines with N,N-dimethylformamide facilitated by water and oxygen

251st National Meeting (2016)

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