Transition from π Radicals to σ Radicals: Substituent‐Tuned Cyclization of Hydrazonyl Radicals

Hydrazonyl radicals are known for their p-electronic structures; however, their s-electronic structures have not been reported as yet. Herein, we show that readily accessible b,g- and g,d-unsaturated N-trichloroacetyl and Ntrifluoroacetyl hydrazones can be conveniently converted into hydrazonyl s radicals, which subsequently undergo 5-exo-trig radical cyclization at the N1 or N2 atom to form pyrazolines and azomethine imines, respectively.