Facile Synthesis of 1,3,7-Trihydroxyxanthone and Its Regioselective Coupling Reactions with Prenal: Simple and Efficient Access to Osajaxanthone and Nigrolineaxanthone F^†

A facile five-step synthesis of naturally occurring 1,3,7-trihydroxyxanthone has been described starting from 1,3,5-trimethoxybenzene via NBS-induced nuclear bromination, lithiation followed by an in situ benzoylation with methyl 2,5-dibenzyloxybenzoate, selective deprotection of the two benzyl groups, base-catalyzed intramolecular cyclization, and demethylations pathway with 62% overall yield. The regioselective coupling reactions of 1,3,7-trihydroxyxanthone with prenal in the presence of calcium hydroxide at room temperature and under thermal conditions at 140−150 °C have been demonstrated to exclusively obtain the natural products osajaxanthone in 75% yield and nigrolineaxanthone F in 98% yield, respectively.