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The cyclization reactions of naphthalene‐fused azo–ene–yne compounds are explored both computationally and experimentally. Calculations reveal that naphtho‐fusion to an azo–ene–yne scaffold does not significantly alter the transition state energies compared to the benzene‐based systems; however, fusing the naphthalene in an angular fashion leads to lower energy intermediates due to the creation of...
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