An Efficient Catalyst for the Synthesis of Pyran

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Mar 6, 2013 - the Synthesis of Pyran Derivatives in Water at Room Temperature, Synthetic ... Keywords Bakers' yeast; dimedone; 4-hydroxy coumarin.
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Fermented Baker's Yeast: An Efficient Catalyst for the Synthesis of Pyran Derivatives in Water at Room Temperature a

M. Saha & A. K. Pal

a

a

Department of Chemistry, North Eastern Hill University, Mawlai Campus, Shillong, India Accepted author version posted online: 08 Aug 2012.Version of record first published: 06 Mar 2013.

To cite this article: M. Saha & A. K. Pal (2013): Fermented Baker's Yeast: An Efficient Catalyst for the Synthesis of Pyran Derivatives in Water at Room Temperature, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 43:12, 1708-1713 To link to this article: http://dx.doi.org/10.1080/00397911.2012.665559

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Synthetic Communications1, 43: 1708–1713, 2013 Copyright # Taylor & Francis Group, LLC ISSN: 0039-7911 print=1532-2432 online DOI: 10.1080/00397911.2012.665559

FERMENTED BAKER’S YEAST: AN EFFICIENT CATALYST FOR THE SYNTHESIS OF PYRAN DERIVATIVES IN WATER AT ROOM TEMPERATURE

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M. Saha and A. K. Pal Department of Chemistry, North Eastern Hill University, Mawlai Campus, Shillong, India

GRAPHICAL ABSTRACT

Abstract An environmentally friendly, one-pot synthesis of biologically important pyran derivatives in water is described herein. The advantages of this method are its simplicity, cost-effectiveness, and environmental friendliness. Water was exploited both as reaction media as well as activator of catalyst (fermentation of bakers’ yeast). Compared with other methods for synthesis of pyran derivatives, satisfactory results were obtained with good yields under simple experimental procedure. Keywords Bakers’ yeast; dimedone; 4-hydroxy coumarin

INTRODUCTION To face current environmental concerns, the development of green organic synthesis is necessary and an environmentally benign protocol appears essential. In these respects, multicomponent reactions (MCRs), particularly those performed in=on aqueous media,[1] have become increasingly useful tools for the synthesis of chemically and biologically important compounds because of their environmentally friendly atom economy and green characteristics.[2] Thus MCRs are perfectly suited Received December 16, 2011. Address correspondence to A. K. Pal, Department of Chemistry, North Eastern Hill University, Mawlai Campus, Shillong 793022, India. E-mail: [email protected]

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for combinatorial library syntheses and are finding increasing use in discovery processes for new drugs and agrochemicals.[3] Pyran derivatives are an important class of compounds, being the main components of many naturally occurring products,[4] and have been of interest in recent years because of their useful biological and pharmacological aspects.[5] These include anticoagulant, anticancer, diuretic, spasmolytic, and anti-anaphylactin activities.[6] They can be used as cognitive enhancers for the treatment of Alzheimer’s disease, Huntington’s disease, amyoprophic lateral sclerosis, Parkinson’s disease, AIDSassociated dementia, and Down syndrome as well as for thetreatment of schizophrenia and myoclonus.[7] These heterocycles are also used as cosmetics, pigments, and biodegradable agrochemicals and photoactive materials.[8] Therefore, several methods have been reported for the synthesis of pyran derivatives using various catalysts and methods such as hexadecyltrimethyl ammonium bromide (HTMAB),[9] benzyltriethylammonium chloride (TEBA),[10] piperidine,[11] N-methylimidazole,[12] (D,L)-proline,[13] sodium carbonate [14] (Na2CO3), dodecylbenzene sulfonic acid (DBSA),[15] KF-alumina,[16] dianilinophthalimide (DAPH),[17] I2,[18] microwave,[19] ultrasound,[20] ionic liquid,[21] 1,8diazabicyclo[5.4.0]undec-7-ene (DBU),[22] potassium phosphate (K3PO4),[23] magnesium oxide (MgO),[24] and sodium dodecyl sulfate (SDS).[25] Although most of these processes offer distinct advantages, at the same time they suffer from certain drawbacks such as longer reaction times, unsatisfactory yields, high costs, harsh reaction conditions, use of a large quantity of volatile organic solvents, expensive metal precursors, and environmentally toxic catalysts. Considering these reports, the development of new, simple, and efficient synthetic methods for the preparation of heterocycles containing pyran ring fragments will be beneficial and an interesting challenge. Bakers’ yeast has the ability to catalyze different type of organic transformation.[26,27] It is also used in the formation of C=C double bonds via acyloin condensation,[28,29] and Michael addition reaction.[30] Because of this important aspect, bakers’ yeast is gaining much importance in organic synthesis.[31] As a part of our current studies on the development of efficient methods for the synthesis of heterocyclic compounds,[32] we herein report an environmentally friendly and straightforward protocol for the synthesis of pyran derivatives by using a biocatalyst (bakers’ yeast) in water at room temperature. RESULTS AND DISCUSSION A number of reactions including Knoevenagel[33] condensation have been carried out in aqueous media. Water is environmentally friendly, safe, and easily available in nature. Therefore we explored the use of water as a solvent for our present work. Accordingly, domino Knoevenagel and Michael addition reaction of dimedone 1 with aryl aldehydes 2 and malononitrile 3 was carried out in an aqueous medium in the presence of biocatalyst (bakers’ yeast) at room temperature. As a model reaction, we selected 1 equiv. of dimedone (1), 1 equiv. of benzaldehyde (2a), 1 equiv. of malononitrile (3), and fermented bakers’ yeast in water at room temperature and obtained a white solid (4a) in 89% yield (Scheme 1, Table 1). The structure of the compound was determined by the analysis of analytical and spectral data.

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Scheme 1. (i) Reagents and conditions: Fermented bakers’ yeast, rt, stirred, 45–60 min.

Scheme 2. (i) Reagents and conditions: Fermented bakers’ yeast, rt, stirred, 0.3–3 h.

In evaluating the effect of catalyst on the model reaction, initially the reaction was carried out without bakers’ yeast and D-glucose and, in another attempt, in the presence of only D-glucose. In both cases, yield of the desired product was very low (23%). A slightly better yield was observed in the presence of bakers’ yeast and Table 1. Synthesis of compounds 4a–k catalyzed by bakers’ yeast at room temperature in water Entry 1 2 3 4 5 6 7 8 9 10 11 a

Ar

3

Product

Time (min)

Yield (%)a

Mp ( C)

C6H5 4-CH3C6H4 4-CH3O C6H4 4-F C6H4 4-NO2C6H4 4-Br C6H4 4N(CH3)2C6H4 4-Cl-C6H4 4-CNC6H4 2-ClC6H4 C10H9

CH2(CN)2 CH2(CN)2 CH2(CN)2 CH2(CN)2 CH2(CN)2 CH2(CN)2 CH2(CN)2 CH2(CN)2 CH2(CN)2 CH2(CN)2 CH2(CN)2

4a 4b 4c 4d 4e 4f 4g 4h 4i 4j 4k

45 55 55 45 45 50 60 50 50 55 60

89 84 87 88 92 90 81 89 90 82 86

230–232 215–217 196–198 189–191 174–176 195–197 198–199 213–215 223–225 212–213 210–211

The yields refer to isolated yields.

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Table 2. Synthesis of compounds 6a–e and 7a–e catalyzed by bakers’ yeast at room temperature in water Entry

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1 2 3 4 5 6 7 8 9 10

Ar

3

Product

Time (h)

Yield (%)a

Mp ( C)

C6H5 4-CH3 C6H4 4-NO2C6H4 4-CH3OC6H4 4-CNC6H4 C6H5 4-NO2C6H4 4-CH3C6H4 4-CH3OC6H4 4-BrC6H4

CH2(CN)2 CH2(CN)2 CH2(CN)2 CH2(CN)2 CH2(CN)2 — — — — —

6a 6b 6c 6d 6e 7a 7b 7c 7d 7e

2.3 3 2 2.3 2.3 0.4 0.3 0.4 0.4 0.3

82 80 85 80 81 87 88 90 86 85

255–256 255–257 250–251 227–229 225–227 228–229 230–232 265–266 245–247 268–270

a

The yields refer to isolated yields.

D-glucose. To improve the yield of the desired product, the reaction was carried out at room temperature by mixing bakers’ yeast and D-glucose in water at pH 7.0. Unfortunately it afforded the desired product 4a in only 39% yield even after prolonged reaction time. On the other hand, the use of fermented bakers’ yeast under the same reaction condition showed a significant improvement of yield as well as reaction time compared to unfermented bakers’ yeast. The best result was achieved by stirring the reaction mixture for 45 min at room temperature using fermented bakers’ yeast. Fermentation was done by stirring a mixture of bakers’ yeast (200 mg) and D-glucose (300 mg) in 5 ml phosphate buffer (pH 7.0) overnight. We next investigated the substrate scope of this domino reaction by subjecting a series of aryl aldehydes 2b–k to the reaction with dimedone 1 and malononitrile 3 in the presence of fermented bakers’ yeast under the optimal condition (Scheme 1). As shown in Table 1, aromatic aldehydes carrying either electron-donating or electron-withdrawing substituents worked well, giving excellent yields of the products with high purity. Encouraged by initial results, we tried to extend the scope of the present protocol for the synthesis of 3,4-dihydropyran[c]chromene derivatives (6a–e). The desired compounds were obtained 81–85% yields by condensation of 1 equiv. of 4-hydroxycoumarin (5), 1 equiv. of aryl aldehydes (2a), and 1 equiv. of malononitrile (3) in the presence of fermented bakers’ yeast in water at room temperature. The results are listed in Table 2. The results clearly indicate that the reaction can tolerate a wide range of differently substituted aryl aldehydes. All products were characterized by elemental analysis, and spectroscopic and physical data (mp) were compared with those reported in literature.12,21,25

CONCLUSION In summary, we have developed a novel, mild, and efficient strategy for the synthesis of pyran derivatives and bis-coumarol from dimedone or 4-hydroxy coumarin, aryl aldehydes, and malononitrile via Knoevenagel condensation followed by Michael addition reaction using fermented bakers’ yeast in water at room temperature. The methodology is environmentally friendly, simple, rapid, and inexpensive, affording good to excellent yields with operational simplicity.

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EXPERIMENTAL

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Melting points were determined in open capillaries and are uncorrected. Infrared (IR) spectra were recorded on Spectrum BX Fourier transform (FT)–IR and Perkin-Elmer (tmax in cm 1) instruments on KBr disks.1H NMR and 13C NMR (400 and 100 MHz respectively) spectra were recorded on Bruker Avance II-400 spectrometer. Mass spectra were recorded on Waters ZQ-4000. CHN were recorded on CHN-OS analyzer (Perkin-Elmer 2400, series II). Silica gel G (E-mark, India) was used for thin-layer chromatography (TLC). Hexane refers to the fraction boiling between 60 and 80  C. Mili-Q-grade water was used for the preparation of phosphate buffer.

Typical Procedure for the Synthesis of Compounds 4a–k and 6a–e A mixture of bakers’ yeast (200 mg), D-glucose (300 mg), and phosphate buffer 5 ml (pH 7.0) was taken in a flask and stirred for 24 h at room temperature. Dimedone 1 (200 mg, 1 mmol) or 4-hydroxy coumarin (162 mg, 1 mmol), aryl aldehyde (1 mmol), and malonitrile 3 (66 mg, 1 mmol) were added to it, and the reaction was continued for the time mentioned in Tables 1 and 2. After completion (TLC), the reaction mixture was diluted with water, extracted with ethyl acetate (10 ml  3), washed with brine (10 ml), and dried over anhydrous sodium sulfate. The solvent was removed in vacuum, and the crude product was purified by column chromatography over silica gel using ethyl acetate–hexane (2:8) as eluent.

Typical Procedure for the Synthesis of Compounds 7a–e A mixture of bakers’ yeast (200 mg), D-glucose (300 mg), and phosphate buffer 5 ml (pH 7.0) was taken in a flask and stirred for 24 h at room temperature. 4-Hydroxy coumarin (324 mg, 2 mmol) and aryl aldehyde (1 mmol) were added to it, and the reaction was stirred for another 30–40 min. After completion (TLC), the reaction mixture was diluted with water, extracted with ethyl acetate (10 ml  3), washed with brine (10 ml), and dried (Na2SO4). The solvent was removed in vacuum, and the crude product was purified by simple recrystallization from ethanol.

ACKNOWLEDGMENTS We thank to the University Grants Commission–Funding for Infrastructure in Science and Technology and Department of Science and Technology–SAP, Department of Chemistry, North Eastern Hill University.

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