Hydrofluoromethylation of alkenes with fluoroiodomethane and beyond

A process for the direct hydrofluoromethylation of alkenes is reported for the first time. This straighforward silyl radical-mediated reaction utilises CH(2)FI as a non-ozone depleting reagent, traditionally used in electrophilic, nucleophilic and carbene-type chemistry, but not as a CH(2)F radical source. By circumventing the challenges associated with the high reduction potential of CH(2)FI being closer to CH(3)I than CF(3)I, and harnessing instead the favourable bond dissociation energy of the C–I bond, we demonstrate that feedstock electron-deficient alkenes are converted into products resulting from net hydrofluoromethylation with the intervention of (Me(3)Si)(3)SiH under blue LED activation. This deceptively simple yet powerful methodology was extended to a range of (halo)methyl radical precursors including ICH(2)I, ICH(2)Br, ICH(2)Cl, and CHBr(2)F, as well as CH(3)I itself; this latter reagent therefore enables direct hydromethylation. This versatile chemistry was applied to (18)F-, (13)C-, and D-labelled reagents as well as complex biologically relevant alkenes, providing facile access to more than fifty products for applications in medicinal chemistry and positron emission tomography.