Radical Reactions of Ynamides

Abstract Ynamides are electron‐rich heteroatom‐substituted alkynes with C−C triple bond directly tethered to the amide group. Over the past decades, ynamides have proven to be versatile reagents for organic synthesis and have received extensive attention. Compared with the well‐established ionic reactions of ynamides, radical‐based ynamide reactions have been exploited relatively seldom. Herein, radical reactions of ynamides, classified by radical attack at the α‐position and β‐position of ynamides, are reviewed by highlighting the reaction selectivity, scope, mechanism, and applicability. The aim of this review is to provide a comprehensive summarization of these advances, casting light on the further development of ynamide chemistry.