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 onepot 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 CÀ P bond formation and CÀ O bond cleavage.

Convergent Deboronative and Decarboxylative Phosphonylation Enabled by the Phosphite Radical Trap “BecaP”

“… 11 While highly reactive aryl radicals add rapidly to trialkyl phosphites, yielding aryl phosphonates after β-scission of the intermediate phosphoranyl radicals, 12 the lower reactivity of alkyl radicals means that they either do not react or undergo unproductive reversible addition. 11a As a result, methods for C–P bond formation from alkyl radicals rely on the use of highly reactive phosphorus reagents, 13 which mainly limits their utility to the synthesis of phosphines, 14 whereas phosphonylations with phosphites to access alkyl phosphonates are limited to highly reactive alkyl radicals, such as bicyclo[1.1.1]butyl radicals. 15 …”

Radical Decarboxylative 1,2,3-Trifunctionalization of 3-Enoic Acids via 1,4-Imino-N Shift: A Modular Approach to Functionalized 3,4-Dihydroisoquinolines

“…8,9 Very recently, we reported a unique dehydroxylative 1,2,4-/1,2,5-trifunctionalization of (bis)homoallylic alcohols by radical 1,4/5-methoxyphosphorous rearrangement mediated C-O bond dissociation to yield phosphorylated fluoroalkyl iodides (Figure 1Ad). 10 However, the existing examples are far from demand and the benefit of olefine long-range multifunctionalization strategies have not been fully appreciated, particularly in the conversion of simple chemicals and precise product-oriented synthesis. Alkenyl carboxylic acids, especially 3-enoic acids, are readily accessible simple building blocks which play important roles in organic transformation.…”