A HClO4‐Catalyzed Substitutive Phosphorylation of Anthracene‐9‐ols with P(O)−H Compounds to Phosphorylated 9,10‐Dihydroanthracenes

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A highly efficient HClO4 catalysed substitutive phosphorylation of S‐, O‐ and N‐based anthracene‐9‐ols with P(O)−H species has been developed to afford phosphorylated 9,10‐dihydroanthracenes with a tetra‐ or trisubstituted carbon centre in good to excellent yields, which serves as a good complement to the established protocols that are limited to tertiary phosphorylated 9,10‐dihydroanthracenes. Gram‐scale synthesis and further elaboration highlight its synthetic utility.