Transient directing ligand- and solvent-controlled C-H/C-H cross-coupling/quaternization cyclization/dequaternization of benzaldehydes with thiophenes.

Rh(iii)-Catalyzed oxidative C-H/C-H cross-coupling between benzaldehydes and thiophenes has been accomplished for the first time. In such reactions, transient directing ligands (TDLs) can not only promote ortho-C-H activation, but can also control the chemoselectivity through a suitable combination of different solvents.