Tuning the Oxidative Mono- or Double-Carbonylation of Alkanes with CO by Choosing a Co or Cu Catalyst

The control of reaction selectivity is a core of organic synthesis, which requires the rational design of the catalytic system. Carbonylation reactions involving CO, such as mono-carbonylation and double-carbonylation, are some of the most powerful tools for constructing carbonyl compounds. However, tunable mono-and double-carbonylation still remain a great challenge, especially for C-H bonds. In this work, we introduced metal-controlled mono-and double-carbonylation reactions of alkanes with amines to prepare alkyl amides and alkyl alpha- ketoamides, respectively (58 examples, yields up to 99%). The Co catalysis system afforded solely monocarbonylation products, and the Cu catalysis system afforded highly selective double-carbonylation products (more than 20:1). Only the choice of the Co or Cu catalyst precursor was the key to producing a dramatic switch in the reaction selectivity.

Automated summary

This work demonstrated metal-controlled mono-and double-carbonylation reactions of alkanes with amines, resulting in the preparation of alkyl amides and alkyl alpha-ketoamides, with Co and Cu catalysis systems affording different selectivities.