TY - JOUR

T1 - Stereoselectivity Inversion by Water Addition in the −SO3H-catalyzed Tandem Prins-Ritter Reaction for Synthesis of 4-amidotetrahydropyran Derivatives

AU - Sidorenko, Alexander Yu

AU - Li-Zhulanov, Nikolai S.

AU - Mäki-Arvela, Päivi

AU - Sandberg, Thomas

AU - Kravtsova, Anna V.

AU - Peixoto, Andreia F.

AU - Freire, Cristina

AU - Volcho, Konstantin P.

AU - Salakhutdinov, Nariman F.

AU - Agabekov, Vladimir E.

AU - Murzin, Dmitry Yu

N1 - Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/5/7

Y1 - 2020/5/7

N2 - 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 °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.

AB - 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 °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.

KW - carbon nanotubes

KW - Prins-Ritter reaction

KW - stereoselectivity

KW - sulfonated materials

KW - tetrahydropyran amides

KW - ACID

KW - DIASTEREOSELECTIVE SYNTHESIS

KW - SEQUENCE

KW - CATALYZED PRINS

KW - 3-COMPONENT

UR - http://www.scopus.com/inward/record.url?scp=85082971905&partnerID=8YFLogxK

U2 - 10.1002/cctc.202000070

DO - 10.1002/cctc.202000070

M3 - Article

AN - SCOPUS:85082971905

VL - 12

SP - 2605

EP - 2609

JO - ChemCatChem

JF - ChemCatChem

SN - 1867-3880

IS - 9

ER -