Traceless Benzylic C−H Amination via BifunctionalN‐Aminopyridinium Intermediates

Abstract 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.