Formal -C(sp³)-H Activation of Ketones via Microwave-Promoted and Iminyl-Radical-Mediated 1,5-Hydrogen Atom Transfer

Microwave irradiation of O-phenyloximes triggersN-O homolysis and 1,5-hydrogen atom transfer (HAT), resultingin formal & gamma;-C-H functionalization of ketones after trappingof the radical intermediate and in situ imine hydrolysis.The Lewis acid InCl3 & BULL;H2O facilitated HAT,enabling functionalization of benzylic and nonbenzylic secondary carbonatoms. Functionalization of primary carbons was feasible but affordedlow yields, requiring ClCH2CO2H instead of InCl3 & BULL;H2O as an additive. C-O and C-Cbond formation could both be accomplished by this method.