Direct Synthesis of N‐formamides by Integrating Reductive Amination of Ketones and Aldehydes with CO2 Fixation in a Metal‐Organic Framework

Abstract Formamides are important feedstocks for the manufacture of many fine chemicals. State‐of‐the‐art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom‐economy. Here, we report the first example of direct synthesis of N‐formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass‐derived aldehydes and ketones, and fixation of CO2 in the presence of H2 over a metal‐organic framework supported ruthenium catalyst, Ru/MFM‐300(Cr). Highly selective production of N‐formamides has been observed for a wide range of carbonyl compounds. Synchrotron X‐ray powder diffraction reveals the presence of strong host‐guest binding interactions via hydrogen bonding and parallel‐displaced π⋅⋅⋅π interactions between the catalyst and adsorbed substrates facilitating the activation of substrates and promoting selectivity to formamides. The use of multifunctional porous catalysts to integrate CO2 utilisation in the synthesis of formamide products will have a significant impact in the sustainable synthesis of feedstock chemicals.