Access to pyrrolines and fused diaziridines by selective radical addition to homoallylic diazirines

Abstract

Pyrroline derivatives are common in bioactive natural products and therapeutic agents. We report here a synthesis of pyrrolines and fused diaziridines by divergent radical cyclization of homoallylic diazirines, which can serve as an internal radical trap and a nitrogen source. This reaction proceeds by selective radical addition to CC or NN bonds followed by intramolecular cyclization. Frontier molecular orbital analysis provides a deep insight into the origin of the selectivity. The reaction demonstrates a new cyclization mode, broad functional group compatibility and high product diversity, and reveals a much broader chemical space for diazirine studies.