An Efficient and Modular Route to C-3*-TunePhos-Type Ligands

An efficient and modular synthetic route to the bidentate C-3*-TunePhos was developed, which allowed tunable steric and electronic effects of the ligands. This novel chemical technology highlights a versatile C-3*-dibromodiphenyl intermediate that was accomplished by in situ Grignard exchange and subsequent Cu(II)-mediated intramolecular oxidative radical coupling process. It is worth noting that this advanced intermediate not only could be easily prepared by a diverse array of C-3*-TunePhos-type ligands, but also could be used to facile synthesis of other novel type of N, S-centered bidentate ligands.