Abstract
Hydroamination has been a steadfast way to install amines onto relatively nonactivated carbon-carbon bonds for decades. The traditional hydroamination of aryl-alkynes requires high temperatures, significantly electron-deficient groups, or catalysts. This work demonstrates that proper alignment of alkynes and nitrogen atoms in pyridine rings allows for enhanced reactivity of hydroamination reactions and is stereoselective for the E-alkene. This was further confirmed by a competition reaction with diethynylpyrazine. The possibility of postsynthetic transformations, such as hydrogenation and alkylation, makes these materials promising nitrogen-rich precursors for other applications.