Metal-Free Bronsted Acid-Catalyzed Rearrangement of δ-Hydroxyalkynones to 2,3-Dihydro-4H-pyran-4-ones: Total Synthesis of Obolactone and a Catechol Pyran Isolated from Plectranthus sylvestris

A metal-free, Bronsted acid, pTsOH-catalyzed intramolecular rearrangement of delta-hydroxyalkynones to substituted 2,3-dihydro-4H-pyran-4-ones was developed. The rearrangement occurs with high regioselectivity under mild and open-air conditions. The scope of work was illustrated by synthesizing an array of aliphatic and aromatic substituted 2,3-dihydro-4H-pyran-4-ones in up to 96% yield, 100% atom economy, and complete regioselectivity. Some of the dihydropyranones are utilized for vinylic halogenations and to complete the total synthesis of bioactive natural products, obolactone and a catechol pyran isolated from Plectranthus sylvestris (Labiatae).