Recent Advances in Single-Electron-Transfer-Mediated Carbonylation

Carbonylation reactions constitute one of the most powerful and widely utilized strategies for synthesizing carbonyl-containing compounds in organic chemistry. Among the mechanistic pathways explored, two-electron transfer (TET) processes have been extensively developed and industrially applied. However, besides their obvious advantages, their intrinsic limitations, such as reliance on precious metal catalysts and restricted compatibility with alkyl substrates, have prompted increasing interest in single-electron transfer (SET) alternatives. Alternatively, SET-mediated carbonylation bypasses the traditional oxidative addition step, generating highly reactive radical intermediates under milder reaction conditions, thus providing enhanced selectivity and broader substrate compatibility. This review offers a comprehensive overview of SET-mediated carbonylation chemistry from 2000 to July 2025, emphasizing mechanistic insights, catalytic systems, and synthetic applications. The objective is to establish a conceptual foundation for understanding recent advances and inspire further exploration into novel reactivity paradigms based on SET strategies within the realm of carbonylation chemistry.