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A highly efficient, green and expeditious solvent-free method is described for the chemoselective conversion of aldehydes to the corresponding acylals in excellent yields, using acetic anhydride in the presence of catalytic amount (20 mol%) of silica-supported LiHSO4. Ketones does not react under these reaction conditions. LiHSO4/SiO2can be recovered and reused without any significant loss of its catalytic activity.

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Trityl chloride (triphenylmethyl chloride, TrCl, Ph3CCl) is utilized as an efficient and homogeneous organocatalyst for the synthesis of 14‐aryl‐14H‐dibenzo[a,j]xanthenes from β‐naphthol and arylaldehydes under solvent‐free conditions. Moreover, a plausible mechanism is suggested based on the literature and on in situ formation of trityl carbocation with inherent instability during the reaction.