Methylation of Arenols through Ni‐catalyzed C—O Activation with Methyl Magnesium Bromide

Direct alkylation of arenols with alkyl organometallic reagents has never been approached. Herein we reported the first successful example of nickel‐catalyzed methylation of arenols with methyl Grignard reagents to construct C(sp²)‐C(sp³) bond under mild conditions. The transformation was compatible with broad substrate scope of 2‐naphthol derivatives. Benzyl alcohol and biphenols were also suitable substrates for this methylation.