The Pseudotransannular Ring Opening of 1-Aminocyclohept-4-ene-derived Epoxides in the Synthesis of Tropane Alkaloids: Total Synthesis of (±)-Ferrugine

Rodriguez, S. ; Uria, U. ; Reyes, E. ; Prieto, L. ; Rodríguez-Rodríguez, M. ; Tejero, T. (Universidad de Zaragoza) ; Merino, P. (Universidad de Zaragoza) ; Vicario, J.L.

Resumen: We have optimized a synthetic approach to (±)-Ferrugine in 8 steps starting from 5-aminocyclohept-1-ene and using the Brønsted acid-catalyzed pseudotransannular ring-opening of the epoxide derived from this cycloheptene as the key step for the construction of the 8-azabicyclo[3.2.1]octane central core. While attempting the enantioselective synthesis of this natural product from enantiopure 2-hydroxy-8-azabicyclo[3.2.1]octane we have found that this compound shows a pronounced tendency to racemize via an achiral symmetric aziridinium intermediate. This racemization side process has been studied in detail using both experimental and computational methods.

Idioma: Inglés

DOI: 10.1002/ejoc.202100332

Año: 2021

Publicado en: European Journal of Organic Chemistry 2021, 20 (2021), 2855-2861
ISSN: 1434-193X

Factor impacto JCR: 3.261 (2021)

Categ. JCR: CHEMISTRY, ORGANIC rank: 19 / 57 = 0.333 (2021) - Q2 - T2

Factor impacto SCIMAGO: 0.738 - Physical and Theoretical Chemistry (Q2) - Organic Chemistry (Q2)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E34-20R
Financiación: info:eu-repo/grantAgreement/ES/MCIU-FEDER-CTQ2017-83633P
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2019-104090RB-100

Tipo y forma: Article (Published version)

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