Traceless Benzylic C−H Amination via Bifunctional N‐Aminopyridinium Intermediates

C−H amination reactions provide the opportunity to streamline the synthesis of nitrogen‐containing organic small molecules. The impact of intermolecular C−H amination methods, however, is currently limited the frequent requirement for the amine precursors to bear activating groups, such as N‐sulfonyl substituents, that are both challenging to remove and not useful synthetic handles for subsequent derivatization. Here, we introduce traceless nitrogen activation for C−H amination—which enables application of selective C−H amination chemistry to the preparation of diverse N‐functionalized products—via sequential benzylic C−H N‐aminopyridylation followed by Ni‐catalyzed C−N cross‐coupling with aryl boronic acids. Unlike many C−H amination reactions that provide access to protected amines, the current method installs an easily diversifiable synthetic handle that serves as a lynchpin for C−H amination, deaminative N−N functionalization sequences. C−H amination chemistry via traceless bifunctional nitrogen activation is reported. Sequential C−H aminopyridylation followed by Ni‐catalyzed cross‐coupling with aryl boronic acids affords the products of aryl nitrene insertion into C−H bonds. These products are unavailable by direct nitrene insertion due to the intrinsic instability of aryl nitrenes. The described method can be applied in the context of pharmacologically active molecules.