Convenient Palladium-Catalyzed Arsination:  Direct Synthesis of Functionalized Aryl Arsines, Optically Active As,N Ligands, and Their Metal Complexes

A convenient recipe for the direct preparation of functionalized tertiary arsines has been developed by simple palladium-catalyzed arsination of aryl triflates using triphenylarsine as the arsinating agent. This catalytic arsination was conducted under neutral reaction conditions and was found to be compatible with various functional groups, such as aldehyde, ester, keto, nitrile, and nitro groups. Interestingly, these reactions can be carried out in either DMF or solvent-free conditions with similar reaction rates and product yields. A notable arsination product, (2-cyanophenyl)diphenylarsine, underwent condensation with optically active 2-aminoalkyl alcohols in the presence of ZnCl₂ catalyst to afford new chiral As,N ligands. The bidentate As,N-free ligand 14 and the Pt-As,N complex 18 were characterized by single-crystal X-ray crystallography.