Energy‐Transfer Enabled 1,4‐Aryl Migration

Abstract Functional group translocation is undoubtedly a pivotal synthetic transformation in organic chemistry. Numerous types of reactions involving radical 1,2‐aryl or 1,4‐aryl migration via electron transfer mechanism have been extensively investigated. Nevertheless, energy‐transfer enabled 1,4‐arylation remains unknown. Herein we disclose that an unprecedented di‐π‐ethane rearrangement featuring 1,4‐aryl migration facilitated by energy transfer catalysis under visible light conditions. The newly developed mild protocol exhibits tolerance towards diverse functional groups and enables the migration of a multitude of aromatic rings, encompassing both electron‐withdrawing and electron‐rich functional groups. The open‐shell strategy has also found successful application in the modification of several drugs. Large‐scale experiments, continuous‐flow experiment, and versatile manipulation of products have demonstrated the robustness and potential utility of this synthetic method. Preliminary mechanistic studies have supported the involvement of radical species in this di‐π‐ethane rearrangement and have also provided evidence for the energy transfer mechanism.