Organocatalytic Enantioselective Nitro-Vinylcyclopropane-Cyclopentene Rearrangement: Expanding the Reactivity of Donor–Acceptor Cyclopropanes

Dedication

Dedicated to Professor Paul Knochel on the occasion of his 70th birthday.

Abstract

The catalytic enantioselective rearrangement of nitro-vinylcyclopropylacetaldehydes has been studied using chiral secondary amines as catalysts. The reaction proceeds through the in situ generation of a donor–acceptor cyclopropane, which rearranges to the corresponding cyclopentene through an open conjugated iminium/unsaturated nitronate intermediate, where the stereochemistry of the starting cyclopropane is lost. This intermediate undergoes an intramolecular Michael reaction in which the asymmetric induction provided by the catalyst allows the preparation of substituted nitrocyclopentenes in good yields and with high stereocontrol. The obtained 2-nitrocyclopentenylacetaldehydes have been transformed into valuable chiral cyclopentenones through Nef reaction with complete retention of the stereochemical information.

Keywords

Enantioselective - Organocatalysis - Rearrangement - Vinylcyclopropane - Cyclopentene - Donor–acceptor cyclopropane - Aldehyde - Nitroolefine

Publikationsverlauf

Eingereicht: 19. Mai 2025

Angenommen nach Revision: 20. Juni 2025

Accepted Manuscript online:
20. Juni 2025

Artikel online veröffentlicht:
31. Juli 2025

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See also:
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