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

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

Journal

Molecular Catalysis
ISSN: 2468-8231

Output data

Year: 2019, Volume: 478, Article number : UNSP 110569, Pages count : DOI: 10.1016/j.mcat.2019.110569

Tags

Organosulfonic clays; Prins reaction; Chromenols; Isopulegol

Authors

Li-Zhulanov Nikolai ^1,3,4 , Maki-Arvela Paivi ¹ , Laluc Mathias ¹ , Peixoto Andreia F. ² , Kholkina Ekaterina ¹ , Sandberg Thomas ¹ , Aho Atte ¹ , Volcho Konstantin ^3,4 , Salakhutdinov Nariman ^3,4 , Freire Cristina ² , Sidorenko Alexander Yu. ⁵ , Murzin Dmitry Yu. ¹

Affiliations

1	(Данные Web of science) Abo Akad Univ, SF-20500 Turku, Finland
2	(Данные Web of science) Univ Porto, Fac Ciencias, Dept Quim & Bioquim, LAQV REQUIMTE, Rua Campo Alegre S-N, P-4169007 Porto, Portugal
3	(Данные Web of science) Novosibirsk Inst Organ Chem, Lavrentjev Ave 9, Novosibirsk 630090, Russia
4	(Данные Web of science) Novosibirsk State Univ, Pirogova St 1, Novosibirsk 630090, Russia
5	(Данные Web of science) Natl Acad Sci Belarus, Inst Chem New Mat, Skaryna Str 36, Minsk 220142, BELARUS

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.

Li-Zhulanov N. , Maki-Arvela P. , Laluc M. , Peixoto A.F. , Kholkina E. , Sandberg T. , Aho A. , Volcho K. , Salakhutdinov N. , Freire C. , Sidorenko A.Y. , Murzin D.Y.
Prins cyclization of (-)-isopulegol with benzaldehyde for production of chromenols over organosulfonic clays
Molecular Catalysis. 2019. V.478. UNSP 110569 . DOI: 10.1016/j.mcat.2019.110569 WOS Scopus РИНЦ

Published print:

Nov 1, 2019

Web of science	WOS:000488138600009
Scopus	2-s2.0-85071402620
Elibrary	41632845
OpenAlex	W2970904653