Synthesis of [60] Fullerene‐Fused Allylbenzofurans via Palladium‐Catalyzed Migration Reaction

Comprehensive Summary Chemical functionalization of fullerenes has been an important topic in fullerene chemistry. Herein, an unprecedented Pd‐catalyzed migration reaction of [60]fullerene with allyloxy‐tethered aryl iodides is present for the preparation of novel [60]fullerene‐fused allylbenzofurans. The use of 1,2‐bis(diphenylphosphino)benzene (DPPBz) as a ligand is crucial for the success of the transformation. The reaction shows high chemo‐ and regioselectivity, and is flexible with regard to allyl‐migration site, providing a new and efficient approach to rare [60]fullerene‐fused benzofurans. Control experiments disclose that the reaction most probably undergoes a sequential C—O bond cleavage/allyl‐migration/intermolecular cycloaddition cascade process.