Regioselective Fluoroalkylphosphorylation of Unactivated Alkenes by Radical-Mediated Alkoxyphosphine Rearrangement.
Angew Chem Int Ed Engl
; 61(30): e202203398, 2022 Jul 25.
Article
em En
| MEDLINE
| ID: mdl-35594364
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/ß-scission on the lone electron pair of phosphorus, resulting in C-P bond formation and C-O bond cleavage.
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MEDLINE
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En
Ano de publicação:
2022
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Article