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The mechanism of the HBr‐catalyzed Friedel‐Crafts‐type reaction between β‐naphthol and HCHO was investigated by DFT to improve this reaction. The HBr‐H2O co‐catalyzed the preferential pathway undergoes the concerted nucleophilic addition and hydrogen shift, stepwise followed by H2O elimination and the CC bond formation. The origin of the high catalytic activity of HBr is ascribed to CH···Br− and...
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