Absence of intermediates in the BINOL-derived MG(II)/phosphate-catalyzed desymmetrizative ring expansion of 1-Vinylcyclobutanols

Capel, Estefanía ; Rodriguez-Rodriguez, Marta ; Uria, Uxue ; Pedron, Manuel (Universidad de Zaragoza) ; Tejero, Tomás (Universidad de Zaragoza) ; Vicario, José L ; Merino, Pedro (Universidad de Zaragoza)

Resumen: The catalyzed desymmetrizative ring expansion of alkenylcyclobutanols promoted by halofunctionalization of the alkene moiety with Nbromosuccinimide has been experimentally and computationally studied. The reaction yields highly enantioenriched cyclopentanones bearing two all-carbon quaternary stereocenters, one of them being generated in the rearrangement of the cyclobutane ring and the other by enantioselective desymmetrization. The reaction is competitive with the formation of a spiroepoxide, but it turns completely selective toward the cyclopentanone when a chiral bisphosphonium magnesium salt is employed as a catalyst. Mechanistic studies support the formation of an ion pair leading to a complex with only a unit of phosphoric acid, which is the resting state of the catalytic cycle. Calculations reproduce in an excellent way the observed reactivity and predict the effect exerted by the substituents of the aromatic ring linked to the double bond. The computational studies also revealed the reaction as a highly asynchronous concerted process taking place as one kinetic step but in two stages: (i) halogenation of the double bond and (ii) rearrangement of the cyclobutane. No intermediates are present in the reaction as energy minima. The experimental scope of the reaction further confirms the predictions for the observed reactivity and selectivity.

Idioma: Inglés

DOI: 10.1021/acs.joc.1c02699

Año: 2022

Publicado en: Journal of Organic Chemistry 87, 1 (2022), 693-707
ISSN: 0022-3263

Factor impacto JCR: 3.6 (2022)

Categ. JCR: CHEMISTRY, ORGANIC rank: 10 / 52 = 0.192 (2022) - Q1 - T1

Factor impacto CITESCORE: 6.8 - Chemistry (Q1)

Factor impacto SCIMAGO: 0.892 - Organic Chemistry (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/MINECO-FEDER/PID2020-118422GB-I00
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-76155-R

Tipo y forma: Article (Published version)

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