Acid-modified Halloysite Nanotubes as a Stereoselective Catalyst for Synthesis of 2H-Chromene Derivatives by the Reaction of Isopulegol with Aldehydes

Acid-modified Halloysite Nanotubes as a Stereoselective Catalyst for Synthesis of 2H-Chromene Derivatives by the Reaction of Isopulegol with Aldehydes Full article

Journal

ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899

Output data

Year: 2018, Volume: 10, Number: 18, Pages: 3950-3954 Pages count : 5 DOI: 10.1002/cctc.201800974

Tags

halloysite; nanotubes; stereoselective catalysis; chromene; acidity

Authors

Sidorenko Alexander Yu. ¹ , Kravtsova Anna V. ¹ , Aho Atte ² , Heinmaa Ivo ³ , Volcho Konstantin P. ⁴ , Salakhutdinov Nariman F. ⁴ , Agabekov Vladimir E. ¹ , Murzin Dmitry Yu. ²

Affiliations

1	(Данные Web of science) Natl Acad Sci Belarus, Inst Chem New Mat, Skaryna Str 36, Minsk 220141, BELARUS
2	(Данные Web of science) Abo Akad Univ, Biskopsgatan 8, SF-20500 Turku, Finland
3	(Данные Web of science) NICPB, Akad Tee 23, EE-12618 Tallinn, Estonia
4	(Данные Web of science) Russian Acad Sci, Novosibirsk Organ Chem Inst, Siberian Branch, Lavrentjev Av 9, Novosibirsk 9630090, Russia

Acid-modified halloysite nanotubes were used for the first time as a stereoselective catalyst for synthesis of oxygen-containing heterocycles applying of allyl alcohol (-)-isopulegol condensation with aldehydes to the octahydro-2H-chromenol (4R- and 4S-diastereomers) as an example. The catalysts were characterized by XRF, XRD, N-2-adsorption, FTIR with pyridine and MAS NMR methods. A high ratio of 4R/4S diastereomers (7.6-14.5) under mild conditions in cyclohexane was considerably exceeding previously reported results. Unprecedented selectivity (79-83%) to 4R isomer of thiophenyl-substituted chromenol exhibiting high analgesic activity was achieved. An increase in stereoselectivity with a decrease in the halloysite drying temperature and catalyst acidity clearly indicates formation of 4R diastereomer on the weak BrOnsted sites. This work is an example that control of the stereoselectivity of acid-catalyzed organic reactions can be effectively carried out by varying water content on the aluminosilicate surface. Modified halloysite nanotubes can be considered as extremely promising catalysts for stereoselective synthesis of heterocyclic compounds.

Sidorenko A.Y. , Kravtsova A.V. , Aho A. , Heinmaa I. , Volcho K.P. , Salakhutdinov N.F. , Agabekov V.E. , Murzin D.Y.
Acid-modified Halloysite Nanotubes as a Stereoselective Catalyst for Synthesis of 2H-Chromene Derivatives by the Reaction of Isopulegol with Aldehydes
ChemCatChem. 2018. V.10. N18. P.3950-3954. DOI: 10.1002/cctc.201800974 WOS Scopus РИНЦ

Published online:	Jul 23, 2018
Published print:	Sep 20, 2018

Web of science	WOS:000445176700003
Scopus	2-s2.0-85050887291
Elibrary	35755058
OpenAlex	W2819626775