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.

Manipulating D–A interaction to achieve stable photoinduced organic radicals in triphenylphosphine crystals

“…The radical anion and radical cation with different stabilities could decay gradually through multiple possible channels, including reacting with oxygen in the atmosphere, [43][44][45][46] back electron-transfer to neutral molecules, 47,48 eliminating halogen in the anion 49,50 and reorganizing radical molecular structures, 51 etc. These complexities should be associated with different evolution trends in the time-dependent EPR spectra.…”

Unlocking the Potential of β-Fragmentation of Aminophosphoranyl Radicals for Sulfonyl Radical Reactions

“…In accordance with the growing focus on radical chemistry, homolytic fragmentation reactions have become increasingly appealing strategies for generating a diverse array of radicals . For example, the employment of phosphoranyl radicals to activate chemical bonds has emerged as one of the most active areas of radical fragmentation research, offering a versatile and tunable approach to access a wide range of radical species, typically through deoxygenation or desulfurization. Furthermore, photocatalysis has provided a streamlined approach for producing phosphoranyl radicals, either by single-electron oxidation of phosphine followed by nucleophilic addition, or via radical addition to phosphine. , …”

Fluoroalkyl Iodides in Fluoroalkylative Difunctionalization of C−C Multiple Bonds

“…In 2022 Han presented a fluoroalkylation-phosphorylation of (bis)homoallylic alcohols, employing fluoroalkyl iodides and phosphine chlorides. [222] A two step one-pot process involve in situ formation of alkoxyphosphine that under CFL irradiation enters a cascade fluoroalkylation process (Scheme 72). A proposed mechanism of the latter involves distal radical rearrangement proceeding through a cyclic intermediate 68.…”