An Environmentally Benign Synthesis of Octahydro-2H-chromen-4-ols via Modified Montmorillonite K10 Catalyzed Prins Cyclization Reaction

Gakul Baishya; Barnali Sarmah; Nabajyoti Hazarika

doi:10.1055/s-0032-1316915

Synlett, Table of Contents

Synlett 2013; 24(9): 1137-1141
DOI: 10.1055/s-0032-1316915

letter

An Environmentally Benign Synthesis of Octahydro-2H-chromen-4-ols via Modified Montmorillonite K10 Catalyzed Prins Cyclization Reaction

Gakul Baishya*

Natural Products Chemistry Division, CSIR-North East Institute of Science & Technology, Jorhat-785006, Assam, India Fax: +91(376)2370011 Email: b.gakul@gmail.com

,

Barnali Sarmah

Natural Products Chemistry Division, CSIR-North East Institute of Science & Technology, Jorhat-785006, Assam, India Fax: +91(376)2370011 Email: b.gakul@gmail.com

,

Nabajyoti Hazarika

Natural Products Chemistry Division, CSIR-North East Institute of Science & Technology, Jorhat-785006, Assam, India Fax: +91(376)2370011 Email: b.gakul@gmail.com

› Author Affiliations

Abstract

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Abstract

(–)-Isopulegol undergoes Prins cyclization reaction in the presence of 20 wt% of acid-treated montmorillonite K10 to produce octahydro-2H-chromen-4-ols in good yields and with high cis selectivities under solvent-free conditions. The solid-acid catalyst can be reused without loss of its activity.

Key words

(–)-isopulegol - Prins cyclization - H-K10 mont - octahydro-2H-chromen-4-ols - reusability

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References

References
1 Nicolaou KC, Sorensen EJ In Classics in Total Synthesis . VCH; Weinheim: 1996

2a Arundale E, Mikeska LA. Chem. Rev. 1952; 51: 505
2b Adams DR, Bhatnagar SP. Synthesis 1977; 661
2c Snider BB In Comprehensive Organic Synthesis . Vol. 2. Trost BM. Pergamon Press; New York: 1991: 527

3a Bratz M, Bullock WH, Overman LE, Takemoto TJ. J. Am. Chem. Soc. 1995; 117: 5958
3b Charonat JA, Nishimura NB, Travers W, Waas JR. Synlett 1996; 1162
3c Pansare SV, Jain RP. Org. Lett. 2000; 2: 175
3d Marumoto S, Jaber JJ, Vitale JP, Rychnovsky SD. Org. Lett. 2002; 4: 3919
3e Cossey KN, Funk RL. J. Am. Chem. Soc. 2004; 126: 12216
3f Dalgard JE, Rychnovsky SD. Org. Lett. 2005; 7: 1589
3g Vitale JP, Wolckenhauer SA, Do NA, Rychnovsky SD. Org. Lett. 2005; 7: 3255
3h Meilert K, Brimble MA. Org. Lett. 2005; 7: 3497
3i Miranda LS. M, Meireles BA, Costa JS, Pereira VL. P. Synlett 2005; 869
3j Barry CS, Busby N, Harding JR, Willis CL. Org. Lett. 2005; 7: 2683
3k Aubele DL, Wan S, Floreancig PE. Angew. Chem. Int. Ed. 2005; 44: 3485 ; Angew. Chem. 2005, 117, 3551
3l Yang X.-F, Wang MW, Zhang Y, Li C.-J. Synlett 2005; 1912
3m Tian X, Jaber JJ, Rychnovsky SD. J. Org. Chem. 2006; 71: 3176
3n Chan K.-P, Ling YH, Loh T.-P. Chem. Commun. 2007; 939
3o Ko HY, Lee DG, Kim MA, Kim HJ, Park JM, Lah S, Lee E. Org. Lett. 2007; 9: 141
3p Yadav JS, Kumar NN, Reddy MS, Prasad AR. Tetrahedron 2007; 63: 2689
3q Yadav JS, Rao PP, Reddy MS, Rao NV, Prasad AR. Tetrahedron Lett. 2007; 48: 1469

4a Yadav JS, Reddy BV. S, Kumar GM, Murthy CV. S. R. Tetrahedron Lett. 2001; 42: 89
4b Crosby SR, Harding JR, King CD, Parker GD, Willis CL. Org. Lett. 2002; 4: 3407
4c Dobbs AP, Martinovic S. Tetrahedron Lett. 2002; 43: 7055
4d Aubele DL, Lee CA, Floreancig PE. Org. Lett. 2003; 5: 4521
4e Liu F, Loh T.-P. Org. Lett. 2007; 9: 2063
4f Tadpetch K, Rychnovsky SD. Org. Lett. 2008; 10: 4839
4g Miranda PO, Carballo RM, Martin VS, Padron JI. Org. Lett. 2009; 11: 357

5a Yadav JS, Subba Reddy BV, Narayana Kumar GG. K. S, Swamy T. Tetrahedron Lett. 2007; 48: 2205
5b Yadav JS, Subba Reddy BV, Narayana Kumar GG. K. S, Reddy MG. Tetrahedron Lett. 2007; 48: 4903
5c Yadav JS, Subba Reddy BV, Maity T, Narayana Kumar GG. K. S. Tetrahedron Lett. 2007; 48: 7155
5d Yadav JS, Subba Reddy BV, Maity T, Narayana Kumar GG. K. S. Tetrahedron Lett. 2007; 48: 8874
5e Yadav JS, Subba Reddy BV, Aravind S, Narayana Kumar GG. K. S, Madhavi C, Kunwar AC. Tetrahedron 2008; 64: 3025
5f Yadav JS, Subba Reddy BV, Narayana Kumar GG. K. S, Aravind S. Synthesis 2008; 395

6 Silva LF. Jr, Quintiliano SA. Tetrahedron Lett. 2009; 50: 2256
7 Yadav JS, Subba Reddy BV, Ganesh AV, Narayan Kumar GG. K. S. Tetrahedron Lett. 2010; 51: 2963

8a Nowrouzi FA, Thadani N, Batey RA. Org. Lett. 2009; 11: 2631
8b Dintzner MR, Mondjinou YA, Unger B. Tetrahedron Lett. 2009; 50: 6639
8c Lu J.-M, Shi M. Tetrahedron 2007; 63: 7545
8d Azizian J, Karimi AR, Kazemizadeh Z, Mohammadi AA, Mohammadizadeh MR. J. Org. Chem. 2005; 70: 1471
8e Bandgar BP, Pandit SS, Sadavarte VS. Green Chem. 2001; 3: 247

9 Wang T, Ma R, Liu L, Zhan Z. Green Chem. 2010; 12: 1576

10a Wallis PJ, Gates WP, Patti AF, Scott JL, Teoh E. Green Chem. 2006; 8: 333
10b Wallis PJ, Gates WP, Patti AF, Scott JL, Teoh E. Green Chem. 2007; 9: 980

11a Hamelin J, Bazureau J-P, Boullet FT In Microwaves in Organic Chemisry . 2nd ed. Loupy A., Wiley-VCH; Weinheim: 2003: Chap. 8,: 253
11b de la Hoz A, Diaz-Ortiz A, Moreno A. Chem. Soc. Rev. 2005; 34: 164
11c Kappe CO. Chem. Soc. Rev. 2008; 37: 1127

12a Loupy A. C. R. Chim. 2004; 7: 103
12b Microwaves in Organic Synthesis . Loupy A. 2nd ed. Wiley-VCH; Weinheim: 2006
12c Strauss CR, Varma RS. Top. Curr. Chem. 2006; 266: 199
12d Varma RS. Green Chem. 1999; 1: 43
12e Varma RS. Pure Appl. Chem. 2001; 73: 193
12f Varma RS. Green Chem. Lett. Rev. 2007; 1: 37
12g Jeselnik M, Varma RS, Polanca S, Kocevar M. Chem. Commun. 2008; 3048

13 Experimental Procedure and Analytical Data Preparation of the Catalyst H-K10 Mont A slurry of commercially available montmorrilonite K10 (5 gm) in 1 M HCl (100 mL) was stirred vigorously at 80 °C for 6 h. The solid was filtered out and washed several times with deionized H₂O to remove Cl^– completely. The solid residue was then dried at 120 °C for 12 h to afford the catalyst. General Procedure for the Synthesis of Octahydro-2H-chromen-4-ol Derivatives A mixture of (–)-isopulegol (1, 1 mmol), an aldehyde 2 (1.2 mmol), and H-K10 mont [20% (wt/wt of 1] were irradiated in a closed vessel in the absence of any solvent in a Synthos 3000 microwave reactor at 360 W for 3 min. After 3 min of reaction time EtOAc was added to the crude reaction mixture, and the mixture was filtered. The residue was further washed with EtOAc to completely remove any product. The EtOAc layer was concentrated under reduced pressure, and the residue was purified by chromatography on silica gel using EtOAc–hexane (3:7) as the eluent to furnish pure the chromenol derivatives 3 and 4. The solid acid catalyst was dried under vacuum and kept in oven at 100 °C before its use for another cycle. The sturctures of the compounds 3a, 4a, 3c, 4c, 3e, 4e, 3f, 4f, 3h, 4h, 3r, 4r, 3s, and 4s were confirmed by comparison of their analytical data with those reported in the literature.⁷ The analytical data of all new compounds are given in the Supporting Information. Selected Analytical Data Compound 3g: viscous liquid. IR (CHCl₃): 3376, 2949, 2924, 2869, 1590, 1562, 1473, 1455, 1377, 1092, 942, 824, 759 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.52 (d, 1 H, J = 8.4 Hz), 7.32 (d 1 H, J = 1.9 Hz), 7.24 (m, 1 H), 4.76 (dd, 1 H, J = 1.4, 11.4 Hz), 3.27 (dt, 1 H, J = 4.2, 10.4 Hz), 2.08–1.93 (m, 2 H), 1.75 (m, 1 H), 1.60 (br s, 1 H, OH), 1.45–1.30 (m, 3 H), 1.32 (s, 3 H), 1.27–0.98 (m, 4 H), 0.94 (d, 3 H, J = 6.4 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 138.7, 133.3, 131.8, 128.8, 128.2, 127.4, 77.6, 73.0, 70.8, 52.1, 48.6, 41.4, 34.3, 31.4, 23.0, 22.2, 21.0. ESI-MS: m/z = 330 [M + 1]⁺. Anal. Calcd for C₁₇H₂₂Cl₂O₂: C, 62.01; H, 6.73. Found: C, 61.96; H, 6.80. Compound 4g: viscous liquid. IR (CHCl₃): 3481, 2926, 2854, 1589, 1563, 1472, 1455, 1375, 1251, 1095, 777 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.50 (d, 1 H, J = 8.4 Hz), 7.31 (d 1 H, J = 2.0 Hz), 7.23 (d, 1 H, J = 1.9 Hz), 5.12 (dd, 1 H, J = 1.7, 11.4 Hz), 3.59 (dt, 1 H, J = 4.0, 11.0 Hz), 1.99–1.94 (m, 2 H), 1.85–1.65 (m, 2 H), 1.55 (br s, 1 H, OH), 1.50–1.40 (m, 2 H), 1.25 (s, 3 H), 1.23–0.96 (m, 4 H), 0.94 (d, 3 H, J = 6.5 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 139.3, 133.1, 132.0, 128.8, 128.3, 127.3, 75.8, 71.2, 69.4, 49.5, 46.6, 41.3, 34.4, 31.2, 28.1, 22.5, 22.2. ESI-MS: m/z = 330 [M + 1]⁺. Compound 3i: white solid; mp 97 °C. IR (CHCl₃): 3387, 2923, 2867, 1597, 1569, 1454, 1376, 1354, 1321, 1206, 1102, 1034, 781, 689 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.45 (s, 1 H), 7.32 (dd, 1 H, J = 1.4, 3.1 Hz), 7.18 (d, 1 H, J = 1.5 Hz), 7.10 (d, 1 H, J = 7.7 Hz), 4.33 (dd, 1 H, J = 2.0, 11.7 Hz), 3.53 (dt, 1 H, J = 4.2, 10.5 Hz), 1.84–1.96 (m, 1 H), 1.82 (dd, 1 H, J = 2.3, 12.8 Hz), 1.20–1.76 (m, 5 H), 1.23 (s, 3 H), 0.95–1.19 (m, 3 H), 0.87 (d, 3 H, J = 6.5 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 145.3, 130.2, 129.8, 129.0, 124.6, 122.5, 75.6, 74.0, 69.4, 49.3, 48.1, 41.2, 34.4, 31.3, 28.2, 22.5, 22.2. ESI-MS: m/z = 362 [M + Na]⁺. Anal. Calcd for C₁₇H₂₃BrO₂: C, 60.18; H, 6.83. Found: C, 60.14; H, 6.81. Compound 4i: semi-solid. IR (CHCl₃): 3455, 2927, 2869, 1597, 1570, 1476, 1455, 1424, 1375, 1327, 1253, 1162, 1097, 1063, 1036, 901, 782, 757 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.53 (s, 1 H), 7.38 (dd, 1 H, J = 1.2, 2.9 Hz), 7.32 (d, 1 H, J = 1.5 Hz), 7.15 (d, 1 H, J = 7.7 Hz), 4.75 (dd, 1 H, J = 2.1, 11.6 Hz), 3.53 (dt, 1 H, J = 4.1, 11.0 Hz), 1.98 (m, 1 H), 1.70–1.80 (m, 1 H), 1.35–1.76 (m, 3 H), 1.24 (s, 3 H), 1.05–1.19 (m, 3 H), 0.96 (d, 3 H, J = 6.5 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 145.3, 130.2, 129.8, 129.0, 124.6, 122.5, 75.6, 74.0, 69.4, 49.3, 48.1, 41.2, 34.4, 31.3, 28.2, 22.5, 22.2. ESI-MS: m/z = 362 [M + Na].

Supplementary Material

Supporting Information