Photoinduced transition-metal- and external-photosensitizer-free intramolecular aryl rearrangement via C(Ar)–O bond cleavage

Abstract

The use of photochemical reactions that do not require expensive photocatalysts or transition metals is an environmentally friendly strategy for accomplishing a variety of structural transformations. Herein, we report a protocol for photoinduced transition-metal- and external-photocatalyst-free intramolecular heteroaryl/aryl rearrangement reactions of 2-heteroaryl/aryloxybenzaldehydes. The protocol was compatible with a variety of functionalities, including methyl, methoxy, cyano, ester, trifluoromethyl, halogen, and heteroaromatic rings. Control experiments suggested that the reaction proceeded via a photoinduced intramolecular heteroaryl/aryl rearrangement process involving photoexcitation of the aldehyde carbonyl group, radical addition, C–C bond formation and C(Ar)–O bond cleavage.