Asymmetric Synthesis of a (P-Chiral) As−P Bidentate Ligand via an Organopalladium Complex Promoted Asymmetric Diels−Alder Reaction between Ph2AsCHCH2 and 1-Phenyl-3,4-dimethylphosphole

Convenient access to the enantiomerically pure rigid bidentate ligand (−)-[5-(diphenylarsino)-2,3-dimethyl-7-phenyl-7( S) -phosphabicyclo[2.2.1]hept-2-ene is established via an asymmetric [4 + 2] cycloaddition between diphenylvinylarsine and 1-phenyl-3,4-dimethylphosphole using the chiral organopalladium(II) complex containing ortho-metalated dimethyl[1-(2-naphthyl)ethyl]amine as the reaction promoter. The absolute configurations of the four newly generated stereocenters have been assigned by single-crystal X-ray analysis.