Photochemical Alkene Hydrophosphination with Bis(trichlorosilyl)phosphine

Abstract

Bis(trichlorosilyl)phosphine (HP(SiCl₃)₂, 1) was prepared from [TBA][P(SiCl₃)₂] ([TBA]2, TBA = tetra-n-butylammonium) and triflic acid in 36% yield. Phosphine 1 is an efficient reagent for hydrophosphination of unactivated terminal olefins under UV irradiation (15-60 min) and gives rise to bis(trichlorosilyl)alkylphosphines (RP(SiCl₃)₂, R = (CH₂)₅CH₃, 88%; (CH₂)₇CH₃, 98%; (CH₂)₂C(CH₃)₃, 76%; CH₂Cy, 93%; (CH₂)₂Cy, 95%; CH₂CH(CH₃)(CH₂)₂CH₃, 82%; (CH₂)₃O(CH₂)₃CH₃, 95%; (CH₂)₃Cl, 83%; (CH₂)₂SiMe₃, 92%; (CH₂)₅C(H)CH₂, 44%) in excellent yields. The products require no further purification beyond filtration and removal of volatile material under reduced pressure. The P-Si bonds of prototypical products RP(SiCl₃)₂ (R = -(CH₂)₅CH₃, -(CH₂)₇CH₃) are readily functionalized to give further phosphorus-containing products: H₃C(CH₂)₇PCl₂ (56%), [H₃C(CH₂)₅P(CH₂Ph)₃]Br (84%), H₃C(CH₂)₇PH₂ (61%), H₃C(CH₂)₅P(O)(H)(OH) (81%), and H₃C(CH₂)₅P(O)(OH)₂ (55%). Experimental mechanistic investigations, accompanied by quantum chemical calculations, point toward a radical-chain mechanism. Phosphine 1 enables the fast, high-yielding, and atom-efficient preparation of compounds that contain phosphorus-carbon bonds in procedures that bypass white phosphorus (P₄), a toxic and high-energy intermediate of the phosphorus industry.