Synthesis of isoxazoline-functionalized phenanthridines via iminoxyl radical-participated cascade sequence.

Readily accessible ß,γ-unsaturated ketoximes reacted with 2-arylphenylisonitriles under the conditions of t-BuOOH and n-Bu4NI to give isoxazoline functionalized phenanthridines via tandem intramolecular/intermolecular C-O/C-C/C-C bond formation. The reaction involves the initial generation of iminoxyl radicals from the oxidation of ß,γ-unsaturated ketoximes by t-BuOOH and n-Bu4NI followed a cascade radical cyclization/addition/cyclization sequence.

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.