SeO<sub>2</sub>-Mediated Oxidative Transposition of Pauson–Khand Products
Sara E. Dibrell, Michael Maser, Sarah E. Reisman
Abstract
Oxidative transpositions of bicyclic cyclopentenones mediated by selenium dioxide (SeO2) are disclosed. Treatment of Pauson–Khand reaction (PKR) products with SeO2 in the presence or absence of water furnishes di- and trioxidized cyclopentenones, respectively. Mechanistic investigations reveal multiple competing oxidation pathways that depend on substrate identity and water concentration. Functionalization of the oxidized products via cross-coupling methods demonstrates their synthetic utility. These transformations allow rapid access to oxidatively transposed cyclopentenones from simple PKR products.
Topics & Concepts
ChemistryPauson–Khand reactionSeleniumOxidative phosphorylationBicyclic moleculeTransposition (logic)Surface modificationCombinatorial chemistrySubstrate (aquarium)StereochemistryOrganic chemistryCatalysisBiochemistryPhysical chemistryOceanographyGeologyLinguisticsPhilosophyCatalytic Alkyne ReactionsAsymmetric Synthesis and CatalysisChemical synthesis and alkaloids