An Umpolung Approach for C2‐Selective C−H Amination of Azines by Palladium Catalysis

Abstract The site‐selective C−H amination of azines is a critical challenge due to the broad applications of amino azines in biologically important compounds. In this work, we report a conceptually novel approach to the electrophilic C2‐selective C−H amination of azines using O ‐benzoylhydroxylamines, catalyzed by a benzyl–palladium complex. A key feature of this transformation is the formation of the distal C−N bond via a benzyl–Pd intermediate, facilitated by a malonate substituent on the azine as a remote directing group. This strategy effectively overrides the inherent polarity mismatch typically observed in electrophilic C2‐C−H aminations. The reaction exhibits high site‐selectivity and demonstrates towards amine‐sensitive functional group, highlighting its synthetic utility.