Metal Effects on the Asymmetric Synthesis of a New Heterobidentate As/P=S Ligand

The cycloaddition reaction between 3,4‐dimethyl‐1‐phenylarsole and diphenylvinylphosphane sulfide was promoted by chiral palladium and platinum complexes containing ortho ‐metalated ( S )‐[1‐(dimethylamino)ethyl]naphthalene. They exhibited similar stereoselectivity; the palladium cycloadducts could not be separated via column chromatography and fractional crystallization, however, the corresponding platinum complexes could be successfully converted into their enantiomerically pure counterpart. A formal arsanylidene elimination reaction was observed on the liberated free As/P=S bidentate ligand.