A Hydrazone Ligand for Iridium-Catalyzed C–H Borylation: Enhanced Reactivity and Selectivity for Fluorinated Arenes

Ir-catalyzed C–H borylations of fluorinated and cyanated arenes with high meta-to-F/CN are described. Use of a dipyridyl hydrazone framework as the ancillary ligand and pinacolborane (HBpin) as the functionalizing reagent generates catalysts that are significantly more active and selective than 4,4′-di-tert-butyl-2,2′-bipyridine (dtbpy) for both electron-deficient and electron-rich substrates. Investigation of the ligand framework resulted in the observation of formal N-borylation of the hydrazone by HBpin, as evidenced by NMR spectroscopy and X-ray crystallography. Subsequent stoichiometric reactions of this adduct with an iridium precatalyst revealed the formation of an unusual Ir^I hydrazido. Isolation and use of this hydrazido reproduce the selectivity of in situ generated catalysts, suggesting that it leads to formation of the active species.