Prins cyclization of (-)-isopulegol with benzaldehyde for production of chromenols over organosulfonic clays

Nikolai Li-Zhulanov, Päivi Mäki-Arvela, Mathias Laluc, Andreia F. Peixoto, Ekaterina Kholkina, Thomas Sandberg, Atte Aho, Konstantin Volcho, Nariman Salakhutdinov, Cristina Freire, Alexander Yu. Sidorenko, Dmitry Murzin

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    6 Citations (Scopus)

    Abstract

    Prins cyclization of (-)-isopulegol with benzaldehyde was investigated with sulphur containing halloysite nanotubes, K10 clays and Cloisite clays. The catalysts were characterized by TEM, SEM, XRD, XPS, pyridine adsorption desorption by FTIR, nitrogen adsorption. The most active catalyst was K10 modified with chlorosulphonic acid giving 95% selectivity to the desired chromenol at 90% conversion and 30 degrees C. Selectivity to chromenol was increasing with increasing Lewis acid site concentration while no linear correlation of chromenol selectivity with the Bronsted acid sites concentration was observed. The diastereoisomer R/S ratio of chromenols was the highest, 11.5, at 70 degrees C and 90% conversion over sulphur modified halloysite nanotubes exhibiting rather low acidity. A higher stability of the R-isomer confirmed by quantum mechanical calculations can partially explain preferential formation of the R diastereomer.Successful catalyst reuse was demonstrated with the best performing catalyst, organosilylated sulphur containing K10.
    Original languageUndefined/Unknown
    Pages (from-to)
    Number of pages12
    JournalMolecular Catalysis
    Volume478
    DOIs
    Publication statusPublished - 2019
    MoE publication typeA1 Journal article-refereed

    Keywords

    • Isopulegol
    • Organosulfonic clays
    • Prins reaction
    • Chromenols

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