Iminoxyl Radical-Promoted Oxycyanation and Aminocyanation of Unactivated Alkenes: Synthesis of Cyano-Featured Isoxazolines and Cyclic Nitrones

A novel and facile approach to vicinal
oxycyanation and aminocyanation
of internal unactivated alkenes is developed. This method utilizes
the dichotomous reactivity of iminoxyl radical derived from the initiation
of β,γ- and γ,δ-unsaturated ketoximes to provide
the general difunctionalization of internal alkenes using tert-butyl hydroperoxide (TBHP) as the environmentally friendly
oxidant, CuCN as the commercially available cyanating reagent, and
penta­methyl­diethyl­ene­triamine (PMDETA) as
the ligand. By using this protocol, a series of useful cyano-featured
isoxazolines and cyclic nitrones were efficiently prepared.