Readily available chiral amine−thioureas are effective catalysts for the first diastereo- and enantioselective epoxidation of unsaturated pyrazolones. The trans- or cis-spiroepoxides are preferentially obtained in good yield and high to excellent enantioselectivity using an appropriate organocatalyst and tert-butyl hydroperoxide as the oxidant. The epoxidation appears applicable to highly challenging β,β′-substituted unsaturated pyrazolones, giving access to spiroepoxides bearing two vicinal quaternary stereocenters. The reaction represents a unique example of Weitz−Scheffer epoxidation, where the catalystcontrolled ring-closure step is usefully exploited to prepare both enantioenriched diastereomeric epoxides.

Diastereodivergent and Enantioselective Access to Spiroepoxides via Organocatalytic Epoxidation of Unsaturated Pyrazolones

MENINNO, SARA;ROSELLI, ANGELO;CAPOBIANCO, AMEDEO;LATTANZI, Alessandra
2017-01-01

Abstract

Readily available chiral amine−thioureas are effective catalysts for the first diastereo- and enantioselective epoxidation of unsaturated pyrazolones. The trans- or cis-spiroepoxides are preferentially obtained in good yield and high to excellent enantioselectivity using an appropriate organocatalyst and tert-butyl hydroperoxide as the oxidant. The epoxidation appears applicable to highly challenging β,β′-substituted unsaturated pyrazolones, giving access to spiroepoxides bearing two vicinal quaternary stereocenters. The reaction represents a unique example of Weitz−Scheffer epoxidation, where the catalystcontrolled ring-closure step is usefully exploited to prepare both enantioenriched diastereomeric epoxides.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11386/4697607
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