Nickel-Catalyzed Alkoxycarbonylation of Aryl Chlorides

We report a nickel(I)-catalyzed alkoxycarbonylation of aryl chlorides with aliphatic alcohols, employing inositol hexaformate (HFI) as a solid CO surrogate and bis(pinacolato)diboron (B2pin2) as a nonmetallic reductant. This protocol enables the efficient synthesis of a broad range of aryl esters from various aryl chlorides, accommodating primary and secondary alcohols as well as phenols with good functional group tolerance. Mechanistic studies indicate that the reaction proceeds through a Ni(I)/Ni(III) catalytic cycle, which circumvents the formation of inactive Ni(CO)4 and addresses the long-standing limitations of conventional Ni(0)/Ni(II) catalysis, including CO-induced deactivation and the high barrier to reductive elimination. Radical-trapping experiments rule out the involvement of diffusible radical intermediates, while nickel oxidation state control experiments disfavor a Ni(0)/Ni(II) manifold. The synthetic utility of this method is demonstrated by the late-stage modification of bioactive molecules and conversion of the resulting esters into amides. Overall, this work provides a sustainable and practical route to aryl esters from inexpensive aryl chlorides, highlighting the potential of Ni(I)/Ni(III) catalysis in carbonylative transformations.