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

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

Journal

Applied Catalysis A: General
ISSN: 0926-860X , E-ISSN: 1873-3875

Output data

Year: 2021, Volume: 618, Article number : 118144, Pages count : DOI: 10.1016/j.apcata.2021.118144

Tags

2H-chromenes; Acidity; DFT; Halloysite; Prins reaction; Terpenoids

Authors

Sidorenko A.Yu. ¹ , Kurban Y.M. ¹ , Il'ina I.V. ² , Li-Zhulanov N.S. ² , Korchagina D.V. ² , Ardashov O.V. ² , Wärnå J. ³ , Volcho K.P. ² , Salakhutdinov N.F. ² , Murzin D.Yu. ³ , Agabekov V.E. ¹

Affiliations

1	Institute of Chemistry of New Materials of National Academy of Sciences of Belarus, Skaryna str, 36, Minsk, 220141, Belarus
2	Novosibirsk Institute of Organic Chemistry, Lavrentjev av. 9, Novosibirsk, 630090, Russian Federation
3	Åbo Akademi University, Biskopsgatan 8, Turku/Åbo, 20500, Finland

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. © 2021 Elsevier B.V.

Sidorenko A.Y. , Kurban Y.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.Y. , Agabekov V.E.
Catalytic synthesis of terpenoid-derived hexahydro-2H-chromenes with analgesic activity over halloysite nanotubes
Applied Catalysis A: General. 2021. V.618. 118144 . DOI: 10.1016/j.apcata.2021.118144 WOS Scopus РИНЦ

Published print:

May 1, 2021

Web of science	WOS:000646252300002
Scopus	2-s2.0-85103753286
Elibrary	46767911
OpenAlex	W3140600096