C7/C8 Functionalization of 1‐Cyanonaphthalenes Through a C8‐Iodination/Catellani Reaction Sequence: A Versatile Route to Highly Functionalized Fluorescent Naphthalenes

We report a concise C8‐iodination/Catellani reaction sequence that provides rapid access to highly functionalized naphthalene scaffolds from simple 1‐cyanonaphthalenes. This modular strategy enables the selective installation of a broad range of substituents at C7‐(amines, aryl groups) and C8‐positions (H, acrylate, vinyl enol ether, alkyne, nitrile), offering a general platform for diversification. Leveraging the versatile reactivity of the cyano group, the method further grants streamlined entry to synthetically valuable naphthalene building blocks and to substituted acenaphtho[1,2‐ b ]pyridines through short post‐functionalization sequences. Moreover, the resulting naphthalene derivatives exhibit tunable blue fluorescence arising from an internal charge‐transfer excited state, highlighting their potential as readily accessible emissive molecular materials. This two‐step approach thus provides a powerful entry to functional naphthalene frameworks relevant to optical and optoelectronic applications.