Abstract
We describe an iridium-catalyzed ortho-selective C–H borylation of unprotected anilines. The employing strong σ-donating cyclometalated mesoionic carbene as C^C bidentate ligand is crucial for the high ortho-selectivity. Computational studies support outer-sphere X–H···Oboryl hydrogen bond interactions, which are strengthened by bidentate C^C ligand introduction. The method shows broad substrate scope and high functional group tolerance.
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