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Synthesis
DOI: 10.1055/a-2640-6415
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Organocatalytic Enantioselective Nitro-Vinylcyclopropane-Cyclopentene Rearrangement; Expanding the Reactivity of Donor-Acceptor Cyclopropanes

Lorena García
1   Department of Organic and Inorganic Chemistry, University of the Basque Country, Leioa, Spain (Ringgold ID: RIN16402)
,
Luisa Carrillo 
2   Organic and Inorganic Chemistry, Universidad del Pais Vasco Facultad de Ciencia y Tecnologia, Leioa, Spain (Ringgold ID: RIN200145)
,
Efraim Reyes 
2   Organic and Inorganic Chemistry, Universidad del Pais Vasco Facultad de Ciencia y Tecnologia, Leioa, Spain (Ringgold ID: RIN200145)
,
Uxue Uria
3   Organic Chemistry and Inorganic Chemistry, Universidad del Pais Vasco Facultad de Ciencia y Tecnologia, Leioa, Spain (Ringgold ID: RIN200145)
,
Liher Prieto 
4   Organic and Inorganic Chemistry, Universidad del País Vasco, Bilbao, Spain (Ringgold ID: RIN16402)
,
Jose Vicario 
5   Department of Organic Chemistry II, Universidad del Pais Vasco, Bilbao, Spain (Ringgold ID: RIN16402)
› Author Affiliations
Supported by: Basque Government IT1558-22
Supported by: Agencia Estatal de Investigación BES-2015-072454,PID2023-146950NB-I00,RED2022-134331-T
Supported by: Euskal Herriko Unibertsitatea N23/30,N23/48
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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 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.



Publication History

Received: 19 May 2025

Accepted after revision: 20 June 2025

Accepted Manuscript online:
20 June 2025

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