# Methane Catalytic Amidation via a Plausible Copper-Nitrene Intermediate

## TL;DR

Scientists developed a new copper-based method to convert methane into amidated compounds without losing hydrogen atoms, using a nitrene intermediate.

## Contribution

The study introduces a novel copper-catalyzed amidation of methane via a nitrene intermediate, a transformation previously unreported for light hydrocarbons.

## Key findings

- Copper-based catalysts enable direct amidation of methane through a nitrene insertion mechanism.
- Mechanistic studies and DFT calculations support a metallonitrene intermediate in the C–H amidation process.
- The method extends to gaseous alkanes and involves sequential hydrogen abstraction and rebound steps.

## Abstract

The catalytic conversion of CH4 into CH3X
compounds has been reported in a few cases, usually involving dehydrogenative
processes in which the H atom is lost. Aiming at expanding this limited
set of transformations, we have investigated the methane amidation
reaction through metal-catalyzed nitrene transfer reactions, a transformation
that remains unreported to date for the lightest hydrocarbon. Herein,
we describe the use of copper-based catalysts for the direct, nondehydrogenative
amidation reaction of methane via a metal-mediated formal nitrene
insertion into the C–H bond, a reaction that is also extended
to the series of gaseous alkanes. Mechanistic studies, supported by
DFT calculations, a microkinetic model, and experimental evidence
have led to the proposal of a metallonitrene intermediate responsible
for this C–H amidation process via sequential hydrogen abstraction
and rebound steps.