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

Li-Zhulanov, Nikolai S.; Mäki‐Arvela, Päivi; Laluc, Mathias; Peixoto, Andreia F.; Kholkina, Ekaterina; Sandberg, Thomas; Aho, Atte; Волчо, К. П.; Salakhutdinov, N. F.; Freire, Cristina; Sidorenko, A.Yu.; Murzin, Dmitry Yu.

doi:10.1016/j.mcat.2019.110569

Cited by 12 publications

(21 citation statements)

References 36 publications

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“…A schematic representation of some investigated solids is given in Figure . Functionalized clays were characterized by TEM, SEM, XRD, XPS, FTIR with pyridine, N 2 adsorption in the previous work . A detailed experimental procedure and characterization results are presented in Supporting Information (SI).…”

Section: Resultsmentioning

confidence: 99%

“…To the best of our knowledge, heterogeneous catalysts for the tandem Prins‐Ritter reaction have not been reported, whereas utilization of homogeneous catalysis is associated with difficulties of the catalyst separation, toxicity and, often, high costs (as triflates, for example). At the same time, heterogeneous materials such as zeolites and modified clays are effective catalysts for Prins cyclization …”

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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A range of heterogeneous -SO 3 H 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 (À )-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 4amidooctahydro-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.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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“…Sulfonic acid functionalized clays were prepared either by direct sulfonation with chlorosulfonic acid (CSA) or by one-pot organosilylation with 2-(4-chlorosulfonylphenyl)-ethyltrimethoxysilane (CSP), as efficient and economically sustainable methodologies to prepare sulfonic acid solid catalysts (Fig. S1) according to previous publications [15,17,18] and also presented in supporting information (SI).…”

Section: Catalyst Synthesis and Characterizationmentioning

confidence: 99%

“…terpenes) using heterogeneous catalysts is very interesting being an environmentally friendly and potentially a cheaper process than alternatives with an easy catalyst reuse and recycling. One important reaction in this context is the Prins cyclization of aldehydes or ketones with alkenes [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. Typically, Prins cyclization is performed by reacting a homoallylic alcohol and carbonyl compounds over acidic catalysts to produce tetrahydropyrans.…”

Section: Introductionmentioning

confidence: 99%

“…Considering that the sulfonated clay based solids with different acidity demonstrated high selectivity in the condensation of isopulegol with benzaldehyde [15], their study for synthesis of acetone-derived chromenol with approved antiviral activity is an actual task. Herein, sulfonic acid-functionalized K-10 and cloisite Na + (CLOI) clay and halloysite nanotubes (HNT) from natural montmorillonites were used as solid acid catalysts for condensation of (−)-isopulegol with acetone.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic synthesis of bioactive 2H-chromene alcohols from (−)-isopulegol and acetone on sulfonated clays

Laluc

Mäki‐Arvela

Peixoto

et al. 2020

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Condensation of (−)-isopulegol with acetone was investigated at 25–40 °C over clay based materials (K10, cloisite Na+ and halloysite nanotubes) modified with sulfonic acid groups by one-pot sulfonation with chlorosulfonic acid or via organosilylation with 2-(4-chlrosulfonylphenyl)-ethyltrimethoxysilane. The target product was the R diastereomer of dimethyl-substituted octahydro-2H-chromen-4-ol with exhibits antiviral activity. The catalysts were characterized by a range of physico-chemical methods. The effect of the initial isopulegol concentrations on the yield of ketone-derived chromenols and the R/S isomers ratio was studied for the first time. The best catalyst was a highly acidic, large pore K10-clay modified by sulfonic acid. Varying the initial concentration of the reagents allows to find a balance between dehydration by-products and a side etherification reaction. A high yield (73%) of the desired chromenols was reached using 0.52 mol/l initial (−)-isopulegol concentration after 240 min at 87% substrate conversion and reaction temperature 25 °C. The yield exceeded that of other previously reported in the open literature catalysts.

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Sulfonic Acid‐Functionalized (Bio)Materials as Catalysts for Efficient Amide Bond Synthesis

et al. 2023

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Sulfonic acid carbon-(bio)based and natural clays-based catalysts were prepared and investigated for the first time as heterogeneous catalysts for amide bond synthesis by a Ritter reaction. The different SO 3 H-catalysts were screened using benzyl alcohol and acetonitrile as model substrates, and MWCNT-CSP revealed to be an efficient catalyst, affording the amide in 75 % yield. The practical utility of the catalysts was demonstrated by a diverse range of amides, obtained from alcohols and nitriles, in moderate to good yields. Biomass derived platform alcohols, such as 5-HMF and furfuryl alcohol, were also tested as potential building blocks for the synthesis of biopolymers. The SO 3 H-catalysts revealed to be a highly efficient and environmentally friendly alternative to the conventional acid catalysts commonly used in the Ritter reaction.

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

Cited by 12 publications

References 36 publications

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

Catalytic synthesis of bioactive 2H-chromene alcohols from (−)-isopulegol and acetone on sulfonated clays

Sulfonic Acid‐Functionalized (Bio)Materials as Catalysts for Efficient Amide Bond Synthesis

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

Cited by 12 publications

References 36 publications

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

Catalytic synthesis of bioactive 2H-chromene alcohols from (−)-isopulegol and acetone on sulfonated clays

Sulfonic Acid‐Functionalized (Bio)Materials as Catalysts for Efficient Amide Bond Synthesis

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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