This review summarizes the recent advances in base-metal-catalyzed carbonylative C—C, C—N, C—O, C—X coupling and other carbonylation reactions of unactivated alkyl electrophiles using CO as C1 source, providing efficient methods for the synthesis of diverse alkyl-substituted carbonyl compounds or their derivatives including ketones, amides, esters, acylsilanes, acylborons, acyl chlorides and alcohols.

Comprehensive Summary

Transition metal-catalyzed carbonylation reactions represent a direct and atom-economical approach to synthesize carbonyl compounds or their derivatives by using CO as a cheap and readily available C1 feedstock. While carbonylation of C(sp²)-hybridized electrophiles (e.g., aryl halides) is well developed, carbonylation of less reactive unactivated alkyl electrophiles remains challenging. Recently, the use of earth-abundant base metals including Cu, Co, Mn, Fe, Ni as catalysts has enabled advances in carbonylative coupling of alkyl electrophiles for approaching diverse carbonyl compounds or their derivatives, notably, some of which are of synthetic importance but difficult to be synthesized through previous reported methods. Herein, we have summarized and discussed these recent achievements in base-metal-catalyzed carbonylative C—C, C—N, C—O, C—X coupling and other carbonylation reactions of unactivated alkyl electrophiles using CO as C1 source.