Organocatalytic Enantioselective Vinylcyclopropane-Cyclopentene (VCP-CP) Rearrangement

Garay, Gorka ; Hurtado, Josebe ; Pedrón, Manuel (Universidad de Zaragoza) ; García, Lorena ; Reyes, Efraim ; Sánchez-Díez, Eduardo ; Tejero, Tomás (Universidad de Zaragoza) ; Carrillo, Luisa ; Merino, Pedro (Universidad de Zaragoza) ; Vicario, Jose L.

Resumen: We have demonstrated that the catalytic and enantioselective vinylcyclopropane-cyclopentene rearrangement can be carried out on (vinylcyclopropyl)acetaldehydes through activation via enamine intermediates. The reaction makes use of racemic starting materials that, upon ring opening facilitated by the catalytic generation of a donor-acceptor cyclopropane, deliver an acyclic iminium ion/dienolate intermediate in which all stereochemical information has been deleted. The final cyclization step forms the rearrangement product, showing that chirality transfer from the catalyst to the final compound is highly effective and leads to the stereocontrolled formation of a variety of structurally different cyclopentenes.

Idioma: Inglés

DOI: 10.1002/anie.202302416

Año: 2023

Publicado en: Angewandte Chemie (International ed.) 62, 22 (2023), e202302416 [7 pp.]
ISSN: 1433-7851

Factor impacto JCR: 16.1 (2023)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 14 / 231 = 0.061 (2023) - Q1 - T1

Factor impacto CITESCORE: 26.6 - Chemistry (all) (Q1) - Catalysis (Q1)

Factor impacto SCIMAGO: 5.3 - Chemistry (miscellaneous) (Q1) - Catalysis (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E34-20R
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2019-104090RB-100
Financiación: info:eu-repo/grantAgreement/ES/MICIU-FEDER/PID2020-118422GB-I00

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)