In Situ‐Generated Cu^I Catalytic System for Oxidative N‐Formylation of N‐Heterocycles and Acyclic Amines with Methanol

The development of a sustainable and simple catalytic system for N-formylation of N-heterocycles with methanol by direct coupling remains a challenge, owing to many competing side reactions, given the sensitivity of N-heterocycles to many catalytic oxidation or dehydrogenation systems. This work concerns the development of an in situ-generated CuI catalytic system for oxidative N-formylation of N-heterocycles with methanol that is based on the case study of a more typical 1,2,3,4-tetrahydroquinoline as substrate. Aside from N-heterocycles, some acyclic amines are also transformed into the corresponding N-formamides in moderate yields. Furthermore, a probable reaction mechanism and reaction pathway are proposed and extension of work based on some findings leads to a demonstration that the formed ⋅O2- and ⋅OOH radicals in the catalytic system is related to the formation of undesired tar-like products.