Photocatalytic Alkyl-to-Aryl Amino Migration

Abstract Functional group migration has served as an emerging strategy for molecular editing in modern organic synthesis. Despite its tremendous success, most research has focused on alkyl-to-alkyl translocations, where a functional group migrates between two varied sites on an alkyl chain. In contrast, the analogous migration from aliphatic to aromatic systems remains a significant challenge. Here, we report a strategy enabling efficient amino group transfer from an alkyl chain directly onto an aromatic ring, thereby overcoming inherent spatial and electronic constraints. The platform showcases broad functional group compatibility and facilitates both 1,4- and 1,5-amino migrations from alkyl to aryl positions. Computational and experimental investigations provide mechanistic insights into the migratory process. This migration strategy enables the direct assembly of structurally diverse aromatic amines and architecturally complex benzolactam derivatives via a streamlined one-pot protocol. Overall, this transformation represents a migratory paradigm that vastly broadens the current functional group migration horizon.