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Described herein is the synthesis of stable oxonium‐doped polycyclic aromatic hydrocarbons (PAHs) by the rhodium‐catalyzed C−H activation/annulations of naphthalene‐type aldehydes with internal alkynes. This protocol provides four divergent reaction types, including two unexpected annulations with an oxygen transposition process, which lead to diverse types of phenalenyl‐fused pyrylium cations comprising...
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