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.