Yttrium‐Catalyzed ortho‐Selective C−H Borylation of Pyridines with Pinacolborane

This work reports a site-selective C-H borylation of pyridines at the ortho-position with pinacolborane enabled by an yttrocene catalyst. The reaction provides a new family of 2-pyridyl boronates with a broad substrate scope and high atom efficiency. The resultant boronates were able to undergo a variety of transformations, e.g., oxidation, Suzuki-Miyaura coupling, Chan-Lam amination and etherification. Catalytic intermediates, including ortho-C-H metalated and borylated complexes, were isolated from stoichiometric experiments and confirmed by single-crystal X-ray diffraction.