文摘
The organopalladium complex containing ortho-metalated (S)-[1-(dimethylamino)ethyl]naphthalene as the chiral template was employed to promote the asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylphosphine. It has been proven that the chiral template incorporating napthylamine is more efficient than the benzylamine based analogue as evidenced by the drastic improvement in stereoselectivity and reaction rate. However, when no chiral template was employed, trans-[PdI2(3,4-dimethyl-1-phenylarsole)2] reacted with trans-[PdI2(diphenylvinylphosphine)2] producing a structurally novel diiodo complex, as a result of an interesting selective cleavage of one As–C bond in the norbornene skeleton and subsequent rearrangements within the skeletal framework. The molecular structure of the diiodo product has been confirmed by X-ray crystallography. Structural analysis showed that in addition to the normal As–P five-membered ring, there is one new five-membered ring containing As–O bond being formed during the course of the reaction along with another seven-membered ring incorporating a hydroxy group.