O-Phenyloximes tethered to alkenes undergo 5-exo-trig iminyl radical cyclizations upon microwave irradiation. Trapping of the resulting cyclic radicals results in C–C, C–N, C–O, C–S, or C–X bond formation. Allylic sulfides undergo a tandem cyclization–thiyl radical β-elimination, affording terminal alkenes. The cyclizations exhibit a broad scope, and in some cases they are highly diastereoselective. The pyrroline adducts are versatile intermediates that can be transformed into a range of different species.

A detailed study of iminyl radical cyclizations of O-aryloximes tethered to alkenes is reported. The reactions can be triggered by either microwave irradiation or conventional heating in an oil bath. A variety of radical traps can be employed, enabling C–C, C–N, C–O, C–S, or C–X bond formation and producing a diverse array of functionalized pyrrolines. Substrates containing an allylic sulfide furnish terminal alkenes by a tandem cyclization–thiyl radical β-elimination pathway. Cyclizations of hydroxylated substrates exhibit moderate diastereoselectivity that in some cases can partially be attributed to intramolecular hydrogen bonding. Computational studies suggested a possible role for thermodynamics in controlling the stereochemistry of cyclizations. The reaction temperature can be lowered from 120 to 100 °C by employing O-(p-tert-butylphenyl)oximes instead of O-phenyloximes as substrates, and these second-generation iminyl radical precursors can be used in a one-pot oxime ether formation–cyclization that is promoted by conventional heating. The functionalized pyrrolines obtained from these reactions can be conveniently transformed in several different ways.

Microwave irradiation of O-phenyloximes triggers N–O homolysis and 1,5-hydrogen atom transfer (HAT), resulting in formal γ-C–H functionalization of ketones after trapping of the radical intermediate and in situ imine hydrolysis. The Lewis acid InCl3·H2O facilitated HAT, enabling functionalization of benzylic and nonbenzylic secondary carbon atoms. Functionalization of primary carbons was feasible but afforded low yields, requiring ClCH2CO2H instead of InCl3·H2O as an additive. C–O and C–C bond formation could both be accomplished by this method.