Catalytic synthesis of terpenoid-derived hexahydro-2H-chromenes with analgesic activity over halloysite nanotubes
| Autor: | N.S. Li-Zhulanov, I. V. Il'ina, Nariman F. Salakhutdinov, O.V. Ardashov, Vladimir Agabekov, D. Yu. Murzin, Yu.M. Kurban, A.Yu. Sidorenko, D. V. Korchagina, Johan Wärnå, Konstantin P. Volcho |
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| Rok vydání: | 2021 |
| Předmět: |
inorganic chemicals
010405 organic chemistry Process Chemistry and Technology Diol Prins reaction Decanal engineering.material 010402 general chemistry 01 natural sciences Medicinal chemistry Halloysite Catalysis 0104 chemical sciences chemistry.chemical_compound chemistry Nucleophile engineering Selectivity Trifluoromethanesulfonate |
| Zdroj: | Applied Catalysis A: General. 618:118144 |
| ISSN: | 0926-860X |
| DOI: | 10.1016/j.apcata.2021.118144 |
| Popis: | 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 Bronsted (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. |
| Databáze: | OpenAIRE |
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