Catalytic Cascade Access to Biaryl‐2‐Methyl Acetates from Pyruvate O ‐Arylmethyl Ketoximes via the Palladium‐Catalyzed C( sp 2 )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( sp 2 )−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( sp 2 )−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.