Catalytic Cascade Access to Biaryl‐2‐Methyl Acetates from Pyruvate O‐Arylmethyl Ketoximes via the Palladium‐Catalyzed C(sp2)H Bond Arylation and C−O Bond Solvolysis

A catalytic cascade has been developed for the synthesis of biaryl‐2‐methyl acetates via a palladium‐catalyzed ortho‐C(sp2)−H bond arylation of pyruvate O‐arylmethyl ketoximes with aryl iodides followed by a solvolysis, in which the pyruvic ketoxime ester as a new auxiliary is employed to direct the C(sp2)−H bond activation. The straightforward treatment of O‐arylmethyl hydroxylamines and ethyl pyruvate with aryl iodides also provides the target products in a one‐pot fashion. Furthermore, the new palladacycle intermediate is unambiguously confirmed by single‐crystal X‐ray diffraction analysis. A plausible reaction pathway is proposed for the Pd‐catalyzed arylation‐acetolysis sequence.