Copper(I)-catalyzed hydrophosphination of styrenes

Hydrophosphination of styrenes has been accomplished with metal salts for the first time. (CuOTf)2·toluene complex is the catalyst of choice, but CuCl can also be used. “In-situ” EPR and NMR studies suggest Cu(I) as the catalytically active metal species, giving exclusively the anti-Markovnikov product. Phosphine oxides or β-ketophosphine oxides can be prepared in one-pot by oxidation with molecular oxygen.

Copper is a selective catalyst for the anti-Markovnikov hydrophosphination of styrenes.Figure optionsDownload as PowerPoint slideResearch highlights
► Hydrophosphination of styrenes is catalyzed by copper salts.
► Tertiary phosphines by Anti-markovnikov addition are exclusively formed.
► Lewis acid and radical pathways contribute to the mechanism of addition.
► Silver and manganese salts are also catalysts for the hydrophosphination.