"Store-and-Release" Strategy Enables Nickel-Catalyzed Deaminative Migratory Arylation of Aliphatic Amines

While migratory functionalization reactions provide a powerful means to navigate broader chemical space, their application to aliphatic amines remains particularly elusive. Herein, we describe the nickel-catalyzed migratory arylation of aliphatic amines using Katritzky salts enabled by a "store-and-release" strategy. This strategy leverages dihydropyridines, which are traditionally viewed as chemical dead-ends under reductive cross-coupling conditions, as latent reservoirs to store and release translocated alkyl radicals, thereby decoupling the chain-walking event from the cross-coupling cycle. The developed protocol enables migratory functionalization of Katritzky salts derived from a wide range of primary amines, and a variety of aryl and heteroaryl bromides. The reaction exhibits broad functional group tolerance, accommodating alkenes, polar functionalities, and substrates derived from pharmaceutically relevant compounds. This methodology enables expanded small-molecule library synthesis through regiodivergent deaminative arylations. Preliminary mechanistic studies support the "store-and-release" design principle, rendering it as a platform that can be applied for other migratory functionalization reactions.