Mesoionic N-heterocyclic olefin catalysed reductive functionalization of CO for consecutive -methylation of amines.

A mesoionic N-heterocyclic olefin (mNHO) was introduced as a metal-free catalyst for the reductive functionalization of CO leading to consecutive double -methylation of primary amines in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN). A wide range of secondary amines and primary amines were successfully methylated under mild conditions. The catalyst sustained over six successive cycles of -methylation of secondary amines without compromising its activity, which encouraged us to check its efficacy towards double -methylation of primary amines. Moreover, this method was utilized for the synthesis of two commercially available drug molecules. A detailed mechanistic cycle was proposed by performing a series of control reactions along with the successful characterisation of active catalytic intermediates either by single-crystal X-ray study or by NMR spectroscopic studies in association with DFT calculations.