Magnesium-catalyzed hydrophosphination of alkenes and alkynes

The hydrophosphination of alkenes and alkynes catalyzed by simple commercially available magnesium reagent was reported. A range of alkenes were converted to the corresponding anti -Markovnikov alkylphosphine products in high yields and high regioselectivity under the presence of 10 mol% Grignard reagent MeMgI at room temperature. Meanwhile, the hydrophosphination of various alkynes was catalyzed by 10 mol% n Bu 2 Mg to afford the corresponding anti -Markovnikov Z -alkenylphosphines with high yields and excellent regioselectivity. Scale-up reaction show great potential in practical applications. • Grignard reagent MeMgI has been employed as an efficient precatalyst for various alkene hydrophosphination. • n Bu 2 Mg has been employed as an efficient precatalyst for various alkyne hydrophosphination. • The magnesium catalyst show a high functional group tolerance and high regioselectivity.