Cu(triNHC)‐Catalyzed N‐Methylation and N‐Formylation of Amines Using CO2

E. Sokolova,Hye‐Young Jang

Published 2025 in ChemistrySelect

ABSTRACT

To address carbon emissions and promote sustainable chemical use, the development of carbon‐utilizing protocols is essential. In this context, leveraging CO2 as a methyl group precursor holds significant potential for broadening its scope in organic reactions. Aiming to reduce the carbon footprint in organic synthesis, we introduce an efficient and selective Cu(triNHC) (triNHC = tri‐N‐Heterocyclic Carbene) catalyst designed for the reduction of CO2 and subsequent N‐methylation and N‐formylation of amines. The triNHC ligand's tridentate chelation is crucial for modulating Cu(triNHC)’s reactivity. This configuration enables direct N‐methylation of amines, bypassing the typical N‐formylation and subsequent reduction pathway. As a result, N‐methylation proceeds faster than in reactions catalyzed by copper catalysts with simpler NHC ligand coordination. Our mechanistic investigations provide support for the proposed reaction pathway, involving CO2 reduction to a methyl precursor followed by its reaction with amines.

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