Resolution of Benzylcyclohexylphenylphosphine by Palladium(II)−Amine Metallacycles. A New Ligand for Asymmetric Hydrovinylation

The synthesis of benzylcyclohexylphenylphosphine and its resolution by means of optically active palladium metallacycles are reported. The absolute configuration of ( R C, S P )-[PdCl(C 6 H 4 CHMeNMe 2 )(PBzCyPh)] has been determined by single-crystal X-ray analyses. The allyl complex [Pd(η 3 -2-MeC 3 H 4 )(PBzCyPh)S]BF 4, prepared in situ from [Pd(η 3 -2-MeC 3 H 4 )Cl(PBzCyPh)] and AgBF 4 in CH 2 Cl 2 solution, was used as a precatalyst for asymmetric hydrovinylation of styrene and 2-vinylnaphthalene. This system permits the synthesis of 3-phenyl-1-butene and 3-(2-naphthyl)-1-butene with good ee values working in very mild conditions of temperature (15 °C).