Azide Radical Initiated Ring Opening of Cyclopropenes Leading to Alkenyl Nitriles and Polycyclic Aromatic Compounds

We report herein a radical‐mediated amination of cyclopropenes. The transformation proceeds through a cleavage of the three‐membered ring after the addition of an azide radical on the strained double bond and leads to tetrasubstituted alkenyl nitrile derivatives upon loss of N2. With 1,2‐diaryl substituted cyclopropenes, this methodology could be extended to a one‐pot synthesis of highly functionalized polycyclic aromatic compounds (PACs). This transformation allows the synthesis of nitrile‐substituted alkenes and aromatic compounds from rapidly accessed cyclopropenes using only commercially available reagents.