The addition of the optically active amines (-)-1-phenylethylamine, (+)-1-phenylethylamine, and (+)-3-aminomethylpinane to diphenylvinylphosphine oxide or 1,1-bis(diphenylphosphino)ethene sulfide gives new PN compounds which were used as cocatalysts in the cross coupling of 1-phenylethyl Grignard with vinylbromide and in the hydrosilylation of acetophenone with diphenylsilane.