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

• Type: Article in International Scientific Journal
• Date: 2020

Authors

Sidorenko, AY (Author) Other; Li Zhulanov, NS (Author) Other; Maki Arvela, P (Author) Other; Sandberg, T (Author) Other; Kravtsova, AV (Author) Other; Peixoto, AF (Author) FCUP; Cristina Freire (Author) FCUP; Volcho, KP (Author) Other; Salakhutdinov, NF (Author) Other; Agabekov, VE (Author) Other; Murzin, DY (Author) Other

Journal

Title: ChemCatChem

Vol. 12 No. 4

Pages: 2605-2609

ISSN: 1867-3880

Publisher: Wiley-Blackwell

Indexing

ISI Web of Knowledge - 8 Citations

Scopus - 10 Citations

Other information

Authenticus ID: P-00R-ZN7

DOI: 10.1002/cctc.202000070

Abstract (EN): 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.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 5