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 β-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 18O-labeling experiments were performed to obtain an insight into various aspects of the controlled reactivity of propargylic hydroperoxides with external nucleophiles under gold catalysis. © 2012 American Chemical Society.Peer Reviewe