Unveiling the Reactivity of Propargylic Hydroperoxides under Gold Catalysis

Controlled gold-catalyzed reactions of primary and secondary propargylic hydroperoxides with a variety of nucleophiles including alcohols, phenols, 2-hydroxynaphthalene-1,4-dione, and indoles allow the direct and efficient synthesis of beta-functionalized ketones. Moreover, the utility of some of the resulting products for the selective preparation of fused polycycles has been demonstrated. In addition, density functional theory (DFT) calculations and O-18-labeling experiments were performed to obtain an insight into various aspects of the controlled reactivity of propargylic hydroperoxides with external nudeophiles under gold catalysis.