Mechanistically Agnostic Aliphatic N–H Transmutations Enabled by Interrupted Nitrogen Deletion

Despite significant recent progress on transmutations of aromatic systems, aliphatic replacements are comparatively underexplored. Herein, we demonstrate three aliphatic transmutations on heteroaryl-fused piperidines via an interrupted nitrogen deletion.

These piperidines react with an anomeric amide to form dearomatized vinylcyclopropanes that can undergo Rh-catalyzed [5 + 1] cycloadditions with carbon monoxide to afford the corresponding cyclohexanone, polar ring-opening in the presence of I₂ and H₂O followed by base-mediated ring closure to give the corresponding dihydropyran, or photochemically promoted radical cyclization with a sulfonothioate to provide the corresponding thiane.