Bronsted Acid-Catalyzed Cycloisomerization of But-2-yne-1,4-diols with or without 1,3-Dicarbonyl Compounds to Tri- and Tetrasubstituted Furans

A Bronsted acid-catalyzed method to prepare tri- and tetrasubstituted furans efficiently from cycloisomerization of but-2-yne-1,4-diols with or without 1,3-dicarbonyl compounds is described. By taking advantage of the orthogonal modes of reactivity of the alcoholic substrate through slight modification of the reaction conditions, a divergence in product selectivity was observed. At room temperature, p-TsOH center dot H2O-mediated tandem alkylation/cycloisomerization of the propargylic 1,4-diol with the beta-dicarbonyl compound was found to selectively occur to provide the tetrasubstituted furan product. On the other hand, increasing the reaction temperature to 80 degrees C was discovered to result in preferential p-TsOH center dot H2O-catalyzed dehydrative rearrangement of the unsaturated alcohol and formation of the 2,3,5-trisubstituted furan adduct.