Stereoselectivity Inversion by Water Addition in the -SO3H-catalyzed Tandem Prins-Ritter Reaction for Synthesis of 4-amidotetrahydropyran Derivatives

Stereoselectivity Inversion by Water Addition in the -SO3H-catalyzed Tandem Prins-Ritter Reaction for Synthesis of 4-amidotetrahydropyran Derivatives Full article

Journal

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

Output data

Year: 2020, Volume: 12, Number: 9, Pages: 2605-2609 Pages count : 5 DOI: 10.1002/cctc.202000070

Tags

Prins-Ritter reaction; tetrahydropyran amides; stereoselectivity; sulfonated materials; carbon nanotubes

Authors

Sidorenko Alexander Yu ^1,2 , Li-Zhulanov Nikolai S. ^1,3,4 , Maki-Arvela Paivi ¹ , Sandberg Thomas ¹ , Kravtsova Anna, V ² , Peixoto Andreia F. ⁵ , Freire Cristina ⁵ , Volcho Konstantin P. ^3,4 , Salakhutdinov Nariman F. ^3,4 , Agabekov Vladimir E. ² , Murzin Dmitry Yu ¹

Affiliations

1	(Данные Web of science) Abo Akad Univ, Biskopsgatan 8, Turku 20500, Finland
2	(Данные Web of science) Natl Acad Sci Belarus, Inst Chem New Mat, Skaryna Str 36, Minsk 220141, BELARUS
3	(Данные Web of science) Novosibirsk Inst Organ Chem, Lavrentjev Av 9, Novosibirsk 630090, Russia
4	(Данные Web of science) Novosibirsk State Univ, Pirogova St 1, Novosibirsk 630090, Russia
5	(Данные Web of science) Univ Porto, Fac Ciencias, Dept Quim & Bioquim, LAQV REQUIMTE, Rua Campo Alegre S-N, P-4169007 Porto, Portugal

A range of heterogeneous -SO3H functionalized catalysts including carbon and halloysite nanotubes, commercial K10 clay, Amberlyst-15 etc. was investigated for the first time using as a model the Prins-Ritter reaction of (-)-isopulegol with benzaldehyde and acetonitrile producing 4-amido derivatives of octahydro-2H-chromenes (as (S)- and (R)-diastereomers). A strong effect of water addition prior the reaction on the overall selectivity and the ratio of isomers in the case of heterogeneous and homogeneous (p-toluenesulfonic acid) catalysis was found for the first time. The yield of the (R)-diastereomer sharply increased with increasing amount of added water, while the S-isomer prevailed with a minimum amount of added water. Experimental results and DFT calculations clearly indicate a kinetic control for R-amide formation. Typically synthesis of 4-amidooctahydro-2H-chromenes requires subzero temperatures and toxic catalysts, which were avoided in the current work. Nevertheless, the yield of the desired products (up to 83 %) at 30 degrees C after water addition exceeded the values reported previously. Thus, adding water is a simple and a very effective method for controlling both the yield and stereoselectivity of the Prins-Ritter reaction products under mild conditions.

Sidorenko A.Y. , Li-Zhulanov N.S. , Maki-Arvela P. , Sandberg T. , Kravtsova A.V. , Peixoto A.F. , Freire C. , Volcho K.P. , Salakhutdinov N.F. , Agabekov V.E. , Murzin D.Y.
Stereoselectivity Inversion by Water Addition in the -SO3H-catalyzed Tandem Prins-Ritter Reaction for Synthesis of 4-amidotetrahydropyran Derivatives
ChemCatChem. 2020. V.12. N9. P.2605-2609. DOI: 10.1002/cctc.202000070 WOS Scopus РИНЦ

Published online:	Mar 27, 2020
Published print:	May 7, 2020

Web of science	WOS:000521798700001
Scopus	2-s2.0-85082971905
Elibrary	43259293
OpenAlex	W3004745676