American Chemical Society
ja071041z_si_001.pdf (9.14 MB)

Domino Electrocyclization/Azide-Capture/Schmidt Rearrangement of Dienones:  One-Step Synthesis of Dihydropyridones from Simple Building Blocks

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journal contribution
posted on 2007-10-03, 00:00 authored by Dong Song, Ali Rostami, F. G. West
Simple 1,4-dien-3-ones undergo Lewis acid-catalyzed Nazarov electrocyclization and intermolecular trapping by various azides to furnish 3,4-dihydropyridin-2-ones in moderate to good yields. The reaction is proposed to proceed via nucleophilic trapping of the 2-oxidocyclopentenyl intermediate, followed by Schmidt-type rearrangement to give a transient 1,4-dipole. In unsymmetrical examples, complete regioselectivity in favor of attack on the less substituted side was observed. The 1,4-dipole intermediate then rearranges to the observed dihydropyridone, via either proton transfer or 1,5-hydride shift.