Selective C–O Bond Reduction and Borylation of Aryl Ethers Catalyzed by a Rhodium–Aluminum Heterobimetallic Complex

We report the catalytic reduction of a C–O bond and the borylation by a rhodium complex bearing an X-type PAlP pincer ligand. We have revealed the reaction mechanism based on the characterization of the reaction intermediate and deuterium-labeling experiments. Notably, this novel catalytic system shows steric-hindrance-dependent chemoselectivity that is distinct from conventional Ni-based catalysts and suggests a new strategy for selective C–O bond activation by heterobimetallic catalysis.