Regioselective Fluoroalkylphosphorylation of Unactivated Alkenes via Radical–Mediated Alkoxylphosphane Rearrangement

02 March 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


A regioselective radical fluoroalkylphosphorylation of unactivated alkenes has been developed by a one-pot twosteps reaction of (bis)homoallylic alcohols, organophosphine chlorides (R2PCl), and fluoroalkyl iodides (RFI) under visible light irradiation. This protocol employs the radical rearrangement of the in situ formed alkoxyphosphane for the first time to regiospecific installing a phosphonyl group onto the inner carbon of terminal olefins in alkene difunctionalization via C-P bond formation and C-O bond homolytic cleavage. Consequently, a series of high value-added fluoroalkylphosphorylated alkyl iodides and alcohols are easily and efficiently synthesized by subsequent iodination and hydroxylation of the generated carbon-centered radicals.


Unactivated Alkenes
Radical rearrangement
One-pot twosteps

Supplementary materials

Supporting Information
Experimental procedures, spectral characterization, crystallographic data, and DFT calculations (PDF)


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