C-N bonds constitute indispensable building blocks of natural products and materials. Especially, N-formyl and N-methyl groups are widely used. However, classical N-formylation and N-methylation methods require reactive formylating and methylating reagents—chloral, phenyl formate, or formic acid for formylating agents, and methyl halide for methylating agents. These reagents accompany by-products that are toxic, non-eco-friendly and produce wastes.<br/>Methanol is recently paid attention as a renewable C1 source. In this regard, we devised a general methodology that can be applied to both N-formylation and N-methylation using methanol as the C1 source. Aliphatic amines selectively give N-formylated, N,N-formylmethylated, N,N-dimethylated amines by changing the reaction conditions with a single ruthenium catalyst. To the best of our knowledge, simultaneous N,N-formylmethylation of amines with methanol is unprecedented until now. Aromatic amines give N-monomethylated amine exclusively under the developed reaction conditions.

Dehydrogenative N-formylation and N-methylation of amines catalyzed by ruthenium pincer complex

253rd National Meeting (2017)

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