Abstract
A dinuclear gold photocatalytic approach for strain-release σ-bond metathesis has been developed by combining inner-sphere electron transfer (ISET) and radical ligand transfer (RLT) mechanisms. This strategy facilitates atom-transfer reactions via C–I bond cleavage, radical translocation, and ligand transfer, yielding a wide range of spirocyclobutyl oxindoles with excellent substrate diversity and atom economy. Additionally, the produced C(sp
3
)–I bond functions as a versatile handle for selective Heck-type coupling with alkenes. Mechanistic investigations indicate a combined ISET-RLT pathway, where sequential excitation and excited-state aurophilic interactions between high-valent gold centers weaken the Au–I bond and enable ligand transfer. Gramscale synthesis and further derivatizations highlight the synthetic utility of this methodology.