The room-temperature hydrophosphinylation of unactivated monosubstituted alkenes using phosphinates (ROP (O) H2) and catalytic NiCl2 in the presence of dppe is described. The method is competitive with prior palladium-catalyzed reactions and uses a much cheaper catalyst and simple conditions. The scope of the reaction is quite broad in terms of unactivated terminal olefins, proceeds at room temperature, often avoids chromatographic ...