The synthesis of tertiary phosphines(III) has been a long-standing challenge in synthetic chemistry because of inevitable issues including harsh conditions, sensitive organometallic reagents, and prefunctionalized substrates in traditional synthesis. Herein, we report a strategically novel C(sp 3 )−H bond phosphorylation that enables the assembly of structurally diverse tertiary phosphines(III) from industrial phosphine(III) sources under mild photocatalytic conditions. The merger of ligand-to-metal charge transfer (LMCT) of FeCl 3 with the hydrogen atom-transfer (HAT) process is the key for the generation of alkyl radicals from hydrocarbons. Strikingly, this catalytic system can be successfully applied for the polymerization of electron-deficient alkenes.

An unprecedented deoxygenative gem-difluorovinylation of aliphatic alcohols with α-trifluoromethyl alkenes is achieved under photocatalytic conditions. Inexpensive Ph3P acts as an efficient O-atom transfer reagent to facilitate the deoxygenation of alcohols...