Catalytic synthesis of terpenoid-derived hexahydro-2H-chromenes with analgesic activity over halloysite nanotubes

[Display omitted] •First systematic study of catalytic terpenoid diol condensation with an aldehydes to bioactive hexahydro-2H-chromene-4,8-diols.•Halloysite nanocatalyst increases both the yields of hexahydro-2H-chromene-4,8-diols and 4S/4R isomers ratio.•Inversion of stereoselectivity with increas...

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Published in:Applied catalysis. A, General General, 2021-05, Vol.618, p.118144, Article 118144
Main Authors: Sidorenko, A.Yu, Kurban, Yu.M., Il'ina, I.V., Li-Zhulanov, N.S., Korchagina, D.V., Ardashov, O.V., Wärnå, J., Volcho, K.P., Salakhutdinov, N.F., Murzin, D.Yu, Agabekov, V.E.
Format: Article
Language:English
Subjects:
2H-chromenes
Acidity
Analgesics
Carbonyl compounds
Carbonyls
Catalysts
Chemical synthesis
Condensates
Dehydration
DFT
Diols
Halloysite
Isomers
Nanotubes
Optimization
Prins reaction
Scandium
Selectivity
Terpenoids
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Summary:[Display omitted] •First systematic study of catalytic terpenoid diol condensation with an aldehydes to bioactive hexahydro-2H-chromene-4,8-diols.•Halloysite nanocatalyst increases both the yields of hexahydro-2H-chromene-4,8-diols and 4S/4R isomers ratio.•Inversion of stereoselectivity with increasing acidity or catalyst drying temperature.•The reaction mechanism is discussed with DFT calculations and kinetic modeling. Condensation of α-pinene derived p-menta-1,8-diene-5,6-diol (diol) with decanal was studied for the first time over modified halloysite nanotubes (HNT). The yield of the desired hexahydro-2H-chromene-4,8-diol with analgesic activity was 76–80 % practically not depending on the catalyst type, while selectivity to 4S-isomer decreased, and to 4R-isomer increased with increasing acidity. The highest selectivity to 4S-diastereomer (48.1 %) on halloysite is a result of weak acidity of this catalyst. DFT optimization of the key intermediate structure shows that the nucleophile attack proceeds at the equatorial position with the 4S-diastereomer formation, which was preferred on halloysite. On strong Brønsted (Amberlyst-15) and Lewis (scandium triflate) acids the target product yield did not exceed 37 % because of dehydration. Halloysite nanocatalysts displayed a stable performance. In the case of diol reaction with a set of carbonyl compounds, the yields of hexahydro-2H-chromene-4,8-diols (up to 88.0%) and the ratio of its 4S/4R isomers (up to 21.0) were significantly higher than on other catalysts.
ISSN:0926-860X
1873-3875
DOI:10.1016/j.apcata.2021.118144