Radical‐Mediated Complete Cleavage of Carbon–Carbon Triple Bonds

Selective cleavage of carbon–carbon triple bonds is a crucial strategy for molecular skeleton reconstruction and functional group introduction in organic synthesis. However, the inherent stability of carbon–carbon triple bonds arising from their high bond energy poses significant challenges to controlled cleavage. Over the past two decades, radical‐mediated cleavage of carbon–carbon triple bonds has emerged as a research hotspot due to its mild reaction conditions, excellent functional group tolerance, and ability to enable difunctionalization. In such reactions, radicals serve to activate the triple bond, mediate intermediate transformations, and directly drive CC bond cleavage, which can efficiently convert alkynes into various carbonyl and functionalized derivatives such as carboxylic acids, aldehydes, ketones, esters, and nitriles. Based on the precursor structure before the cleavage of the final CC bond of the carbon–carbon triple bond, this review classifies radical‐mediated cleavage reactions of carbon–carbon triple bonds into aldehydes/ketones, ketoacids, diketones, four‐membered rings, and five‐membered rings. It systematically summarizes the latest research progress in this field, thoroughly discusses radical initiation methods, reaction mechanisms, and control experiments, as well as highlights their synthetic applications.