Regioselective Fluoroalkylphosphorylation of Unactivated Alkenes via Radical–Mediated Alkoxylphosphane Rearrangement

Dong-Tai Xie; Hong-Lei  Chen; Dian  Wei; Bang-Yi  Wei; Zheng-Hu  Li; Jian-Wu  Zhang; Wei  Yu; Bing Han

doi:10.26434/chemrxiv-2022-vnh52

Organic Chemistry

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Regioselective Fluoroalkylphosphorylation of Unactivated Alkenes via Radical–Mediated Alkoxylphosphane Rearrangement

Working Paper

Dong-Tai Xie State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University ,
Hong-Lei Chen State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University ,
Dian Wei State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University ,
Bang-Yi Wei State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University ,
Zheng-Hu Li State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University ,
Jian-Wu Zhang State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University ,
Wei Yu State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University ,
Bing Han State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University

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Abstract

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.