Asymmetric synthesis of 1,2-bis(diphenylphosphino)-1-phenylethane via a chiral palladium template promoted hydrophosphination reaction

An organopalladium(II) complex derived from (S)-N,N-dimethyl-1-(1-naphthyl)-ethylamine was employed as the chiral auxiliary to promote the asymmetric hydrophosphination reactions between diphenylphosphine and (E) or (Z)-diphenylphosphinostyrene in high regio- and stereoselectivities at low temperature with triethyl amine as external base. Optically active free ligand (R)-1,2-bis(diphenylphosphino)-1-phenylethane was obtained in high yield subsequently. Mechanistic pathways explaining the stereoselectivity of the chiral organopalladium template promoted hydrophosphination reactions are also proposed.

Graphical abstractAn organopalladium(II) complex derived from (S)-N,N-dimethyl-1-(1-naphthyl)-ethylamine was employed as the chiral auxiliary promoted the asymmetric hydrophosphination reactions between diphenylphosphine and (E) or (Z)-diphenylphosphinostyrene yielding the optically pure ligand (R)-1,2-bis(diphenylphosphino)-1-phenylethane in high yield. Mechanistic pathways explaining the stereoselectivity of the reactions are also proposed.Figure optionsDownload full-size imageDownload as PowerPoint slide