This review carefully summarizes the advances achieved in catalytic hydrofunctionalization of ynamides and is categorized by the bond formation type including C−C, C−X, C−O, C−N, C−S, C−P, C−Si, and C−Ge bonds.
Under photoredox- and piezo-catalysis conditions, ynamides undergo a radical to yield polycyclic compounds by fully utilizing the ynamide unsaturations.
Metal-free [2 + 2] and [4 + 2] self-cycloadditions of N-aryl-substituted ynamides provide various valuable functionalized aminocyclobutenes and 4-aminoquinoline derivatives.
Computational studies shed light on why the incorporation of Au(I)-catalyst, a nitrogen atom and tosylamide group into heptatrienyl cations allows it to undergo 6π electrocyclization to afford seven-membered azepine instead of five-membered pyrrole product.
Our metal-free, switchable synthesis using light or heat transforms ynamides into valuable α-sulfonyl amides or nitriles, providing a sustainable toolkit.