Catalytic hydrophosphination of styrenes

[reaction: see text] The first example of intermolecular hydrophosphination of styrenes catalyzed by Ni and Pd complexes is described. The reaction of Ph2PH with styrene, 4-vinylpyridine, 2-vinylpyridine, 4-methoxystyrene, 2-methoxystyrene, and 5-vinyl-2-methylpyridine in benzene under Ni[P(OEt)3]4 catalysis proceeds with high yield and selectivity to give only anti-Markovnikov product.