Regioselective Fluoroalkylphosphorylation of Unactivated Alkenes by Radical‐Mediated Alkoxyphosphine Rearrangement**

Abstract A novel distal radical rearrangement of alkoxyphosphine is developed for the first time and applied to the regioselective radical fluoroalkylphosphorylation of unactivated olefins. By employing a one‐pot two‐step reaction of (bis)homoallylic alcohols, organophosphine chlorides, and fluoroalkyl iodides under CFL (compact fluorescence light) irradiation, a series of fluoroalkylphosphorylated alkyl iodides and alcohols are easily synthesized by regiospecific installing a phosphonyl onto the inner carbon of terminal olefins and further iodination/hydroxylation. Mechanism studies reveal that the migration undergoes a distinctive radical cyclization/β‐scission on the lone electron pair of phosphorus, resulting in C−P bond formation and C−O bond cleavage.