Brønsted acid catalyzed Prins-Ritter reaction for selective synthesis of terpenoid-derived 4-amidotetrahydropyran compounds
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Altres documents de l'autoria: Sidorenko, A. Yu; Kurban, Yu.M.; Peixoto, A.F.; Li-Zhulanov, N.S.; Sánchez-Velandia, Julián E.; Aho, A.; Wärnå, Johan; Gu, Yu; Volcho, Konstantin; Salakhutdinov, Nariman; Murzin, D.Yu; Agabekov, Vladimir
Metadades
Mostra el registre complet de l'elementcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7053
comunitat-uji-handle3:10234/8639
comunitat-uji-handle4:
INVESTIGACIONMetadades
Títol
Brønsted acid catalyzed Prins-Ritter reaction for selective synthesis of terpenoid-derived 4-amidotetrahydropyran compoundsAutoria
Data de publicació
2023-01-05Editor
ElsevierISSN
0926-860X; 1873-3875Cita bibliogràfica
A. Yu. Sidorenko, Y. M. Kurban, A. F. Peixoto, N. S. Li-Zhulanov, J. E.Sánchez-Velandia, A. Aho ,J. Wärnå, Y. Guf, K. P. Volcho,N. F.Salakhutdinov, . Yu. Murzin, V. E. Agabekov, Brønsted acid catalyzed Prins-Ritter reaction for selective synthesis of terpenoid-derived 4-amidotetrahydropyran compounds,Applied Catalysis A, General 649 (2023) 118967.Tipus de document
info:eu-repo/semantics/articleVersió de l'editorial
https://www.sciencedirect.com/science/article/pii/S0926860X22004902Versió
info:eu-repo/semantics/publishedVersionParaules clau / Matèries
Resum
A number of SO3H-functionalized solids (biochar, montmorillonites, carbon and halloysite nanotubes) has been studied as catalysts in the cascade Prins-Ritter reaction of (-)-isopulegol with benzaldehyde and acetonitrile ... [+]
A number of SO3H-functionalized solids (biochar, montmorillonites, carbon and halloysite nanotubes) has been studied as catalysts in the cascade Prins-Ritter reaction of (-)-isopulegol with benzaldehyde and acetonitrile for synthesis of octahydro-2H-chromene amides (as 4R- and 4S-isomers). A high selectivity to these products at 30 °C in the presence of H2O was observed on catalysts modified with chlorosulfonic acid (CSA) reaching 84% (4R/4S of 5.7) in the case of biochar, while a relatively large amount of octahydro-2H-chromenols (up to 31%), products of Prins condensation, was formed on the materials functionalized by 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane (CSP). Although Prins condensation proceeds efficiently on weak acid sites, the Prins-Ritter reaction requires sulfated materials with strong (0.33 – 5.8 mmol/g) Brønsted acidity. Catalysts functionalized by CSP were stable, while for the materials modified with chlorosulfonic acid, leaching of -SO3H groups was observed. Nonetheless, on resistant Bioсhar-CSP, selectivity to the amides at 30 °C (67%) was higher than that with the commercial Amberlyst-15 (47%), and triflic acid at − 25 °C (62%). Similar selectivity to the desired products on Biochar-CSA (-SO3H groups) and H2SO4 (81–84%) as well as on Biochar-CSP (-PhSO3H) and with p-toluenesulfonic acid (67–70%) was observed. DFT calculations and experimental results showed that at 30 °C formation of 4S-amide thermodynamically is more beneficial than of alcohols and dehydration products. However, addition of water results in a sharp increase in the reaction rate and 4R-amide selectivity due to a change to the kinetic control, leading eventually to both high yields and stereoselectivity. The proposed reaction pathways also were confirmed by kinetic modelling. [-]
Publicat a
Applied Catalysis A: General, 2023, vol. 649Entitat finançadora
National Academy of Sciences of Belarus | Universitat Jaume I | undação para a Ciência e a Tecnologia (FCT/MCTES)
Codi del projecte o subvenció
UIDB/50006/2020 | UIDP/50006/2020 | 2020.01614.CEECIND/CP1596/CT0007
Drets d'accés
info:eu-repo/semantics/openAccess
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