Light-Switchable Dicarbonylation of Terminal Alkynes: Access to Maleamides and 1,3-Disubstituted Maleimides with Retention of C═C Double Bond

Abstract Palladium-catalyzed double aminocarbonylation of terminal alkynes provides access to unsaturated dicarbonyl compounds, yet conventional systems generate metal-hydride species, causing C═C over-reduction and poor stereocontrol. We report a ligand-regulated Pd-catalyzed double aminocarbonylation of terminal alkynes with CO and amines under mild, oxidant-free conditions affords exclusively Z-maleamides; blue light triggers cyclization to maleimides. Mechanistic studies show in situ generated H–Pd–Br preferentially reacts with aniline, avoiding alkyne hydrometalation. This light-switchable protocol enables divergent chemoselective synthesis of maleamides and maleimides.