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

An in situ-generated Cu^I catalytic system is developed for oxidative N-formylation of N-heterocycles by direct cross-coupling with methanol. Moreover, some acyclic amines are also transformed into the corresponding N-formamides in moderate yields. A likely reaction mechanism and reaction pathway are also proposed.

Abstract

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 Cu^I 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.

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