Synlett, Table of Contents Synlett 2013; 24(5): 581-586DOI: 10.1055/s-0032-1318406 letter © Georg Thieme Verlag Stuttgart · New YorkNitrosyl Tetrafluoroborate Catalyzed Preparation of 2,3-Unsaturated Glycosides and 2-Deoxyglycosides of Hindered Alcohols, Thiols, and Sulfonamides Authors Author Affiliations Abhishek Santra Division of Molecular Medicine, Bose Institute, P-1/12, C. I. T. Scheme VII M, Kolkata 700054, India Fax: +91(33)23553886 Email: akmisra69@gmail.com Goutam Guchhait Division of Molecular Medicine, Bose Institute, P-1/12, C. I. T. Scheme VII M, Kolkata 700054, India Fax: +91(33)23553886 Email: akmisra69@gmail.com Anup Kumar Misra* Division of Molecular Medicine, Bose Institute, P-1/12, C. I. T. Scheme VII M, Kolkata 700054, India Fax: +91(33)23553886 Email: akmisra69@gmail.com Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract Nitrosyl tetrafluoroborate (NOBF4) has been successfully applied as an efficient organocatalyst for the preparation of 2,3-unsaturated and 2-deoxyglycosides of hindered alcohols, aryl thiols, and aryl sulfonamides from glycal derivatives under the Ferrier rearrangement conditions. Product yields and stereo-outcomes were very good. Key words Key wordsglycal - Ferrier rearrangement - NOBF4 - 2,3-unsaturated glycoside - 2-deoxyglycoside Full Text References References and Notes 1 Danishefsky SJ, Bilodeau MT. Angew. Chem., Int. Ed. Engl. 1996; 35: 1380 2 Fraser-Reid B. Acc. Chem. Res. 1985; 18: 347 3 Holder NL. Chem. Rev. 1982; 82: 287 4 Ferrier RJ. Topics Curr. Chem. 2001; 215: 153 5 Liu ZJ, Zhou M, Min JM, Zhang LH. Tetrahedron: Asymmetry 1999; 10: 2119 6 Bussolo VD, Kim YJ, Gin DY. J. Am. Chem. Soc. 1998; 120: 13515 7 Remers WA In The Chemistry of Antitumor Antibiotics . Wiley-Interscience; New York: 1979: 133-175 8 Toshima K, Tatsuda K. Chem. Rev. 1993; 93: 1503 9 Matsumoto K, Ebata T, Matsushita H. Carbohydr. Res. 1995; 267: 187 10 Fakha G, Sinou D. Molecules 2005; 10: 859 11 Tiwari P, Misra AK. J. Org. Chem. 2006; 71: 2911 12 Cardona F, Valenza S, Picasso S, Goti A, Brandi A. J. Org. Chem. 1998; 63: 7311 13 Klaffke W, Pudlo P, Springer D, Thiem J. Liebigs Ann. Chem. 1991; 6: 509 14 Bhate P, Horton D, Priebe W. Carbohydr. Res. 1985; 144: 331 15 Toshima K, Ishizuka T, Matsuo G, Nakata M. Chem. Lett. 1993; 2013 16 Babu BS, Balasubramanian KK. Tetrahedron Lett. 2000; 41: 1271 17 Koreeda M, Houston TA, Shull BK, Klemke E, Tuinman RJ. Synlett 1995; 90 18 Takhi M, Abdel-Rahman AA.-H, Schmidt RR. Tetrahedron Lett. 2001; 42: 4053 19 Yadav JS, Reddy BV. S. Synthesis 2002; 511 20 Lopez JC, Gomez AM, Valverdi S, Fraser-Reid B. J. Org. Chem. 1995; 60: 3851 21 Hou D, Lowary TL. Carbohydr. Res. 2009; 344: 1911 ; and references cited therein 22 Yadav JS, Reddy BV. S, Reddy KB, Satyanarayana M. Tetrahedron Lett. 2002; 43: 7009 23 Chandrasekhar S, Reddy CR, Chandrashekar G. Tetrahedron Lett. 2004; 45: 6481 24 Colinas PA, Bravo RD. Carbohydr. Res. 2007; 342: 2297 25 Témpera CA, Colinas PA, Bravo RD. Tetrahedron Lett. 2010; 51: 5372 26 Ding F, William R, Gorityala BK, Ma J, Wang S, Liu XW. Tetrahedron Lett. 2010; 51: 3146 27 Rodríguez OM, Colinas PA, Bravo RD. Synlett 2009; 1154 28 Misra AK, Tiwari P, Agnihotri G. Synthesis 2005; 260 29 Levecque P, Gammon DW, Jacobs P, De Vos D, Sels B. Green Chem. 2010; 12: 828 30 Das SK, Reddy KA, Roy J. Synlett 2003; 1607 31 Sau A, Santra A, Misra AK. Synlett 2012; 23: 2341 32 Priebe W, Zamojski A. Tetrahedron 1980; 36: 287 33 Dunkerton LV, Adair NK, Euske JM, Brady KT, Robinson PD. J. Org. Chem. 1988; 53: 845 34 Jordan MA, Wilson L. Nat. Rev. Cancer 2004; 4: 253 35 Supuran CT. Exp. Opin. Invest. Drugs 2003; 12: 283 36 Ferrier RJ, Zubkov OA. Org. React. 2003; 62: 569 37 Colinas PA, Bravo RD. Org. Lett. 2003; 5: 4509 38 Tilve RD, Alexander MV, Khandekar AC, Samant SD, Kanetkar VR. J. Mol. Catal. A: Chem. 2004; 223: 237 39 Bettadaiah BK, Srinivas P. Tetrahedron Lett. 2003; 44: 7257 40 Guchhait G, Misra AK. Catal. Lett. 2011; 141: 925 41 Brown DS, Ley SV, Vile S, Thompson M. Tetrahedron 1991; 47: 1329 42 Reddy BV. S, Divyavani C, Yadav JS. Synthesis 2010; 1617 43 Grynkiewicz G, Priebe W, Zamojski A. Carbohydr. Res. 1979; 68: 33 44 Banaszek A, Zamojski A. Polish J. Chem. 1979; 53: 2029 45 Spectral data of the products those are not reported earlier are as follows. 5-Methyl-2-hexyl 4,6-Di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyranoside (4) 1H NMR (500 MHz, CDCl3): δ = 5.78–5.71 (m, 1 H, H-2), 5.69–5.66 (m, 1 H, H-3), 5.23–5.20 (m, 1 H, H-4), 5.05 (br s, 1 H, H-1), 4.19–4.10 (m, 2 H, H-6ab), 4.02–3.98 (m, 1 H), 1.99, 1.96 (2 s, 6 H, 2 COCH3), 1.72–1.58 (m, 1 H), 1.48–1.38 (m, 2 H), 1.18 (br s, 3 H), 1.13–1.07 (m, 2 H), 0.89, 0.84 (2 s, 6 H). 13C NMR (125 MHz, CDCl3): δ = 170.7, 170.2, 129.0, 128.4, 91.2, 67.1, 65.2, 63.4, 47.5, 25.0, 23.1, 23.0, 22.9, 22.5, 21.0, 20.8, 20.1. ESI-MS: m/z = 351.1 [M + Na]+. Anal. Calcd for C17H28O6 (328.18): C, 62.17; H, 8.59. Found: C, 62.02; H, 8.80. Cholesteryl 3,4,6-Tri-O-acetyl-2-deoxy-α-d-galactopyranoside (16) 1H NMR (500 MHz, CDCl3): δ = 5.28–5.23 (m, 2 H, H-1, H-3), 5.08 (br s, 1 H, H-4), 4.17–4.15 (m, 1 H, H-5), 4.04–3.97 (m, 2 H, H-6ab), 3.40–3.30 (m, 1 H), 2.26–2.21 (m, 1 H), 2.16 (s, 3 H, COCH3), 2.03–1.98 (m, 1 H, H-2e), 1.97, 1.90 (2 s, 6 H, 2 COCH3), 1.92–1.86 (m, 1 H, H-2a), 1.80–0.60 (m, 43 H, cholesterol). 13C NMR (125 MHz, CDCl3): δ = 170.4, 170.1, 170.0, 140.7, 121.9, 95.7, 77.3, 66.9, 66.7, 66.4, 62.7, 56.7, 56.1, 50.2, 42.3, 40.0, 39.8, 39.5, 37.1, 36.7, 36.2, 35.8, 31.9, 31.8, 30.7, 28.2, 28.0, 27.9, 24.3, 23.8, 22.8, 22.6, 21.0, 20.9, 20.8, 20.7, 19.3, 18.7, 11.8. ESI-MS: m/z = 681.4 [M + Na]+. Anal. Calcd for C39H62O8 (658.44): C, 71.09; H, 9.48. Found: C, 70.91; H, 9.66. Benzenesulfonamido 3,4,6-Tri-O-acetyl-2-deoxy-α-d-galactopyranoside (17) 1H NMR (500 MHz, CDCl3): δ = 7.86–7.82 (m, 2 H, ArH), 7.51–7.40 (m, 2 H, ArH), 6.70 (d, J = 7.5 Hz, 1 H, NH), 5.45–5.43 (m, 1 H, H-1), 5.19–5.15 (m, 1 H, H-3), 5.11 (br s, 1 H, H-4), 3.71–3.67 (m, 1 H, H-6a), 3.62–3.59 (m, 1 H, H-6b), 3.14–3.12 (m, 1 H, H-5), 2.25–2.19 (m, 1 H, H-2e), 2.00, 1.98, 1.78 (3 s, 9 H, 3 COCH3), 1.80–1.74 (m, 1 H, H-2a). 13C NMR (125 MHz, CDCl3): δ = 171.2, 170.2, 170.1, 141.1-126.7 (ArC), 79.1, 66.7, 65.7, 65.5, 60.8, 29.3, 20.8, 20.7, 20.6. ESI-MS: m/z = 452.1 [M + Na]+. Anal. Calcd for C18H23NO6S (429.11): C, 50.34; H, 5.40. Found: C, 50.26; H, 5.57. p-Toluenesulfonamido 3,4,6-Tri-O-acetyl-2-deoxy-β-d-galactopyranoside (18) 1H NMR (500 MHz, CDCl3): δ = 7.71–7.69 (m, 2 H, ArH), 7.21–7.17 (m, 2 H, ArH), 6.28 (d, J = 7.6 Hz, 1 H, NH), 5.12 (d, J = 3.0 Hz, 1 H, H-4), 4.94–4.89 (m, 1 H, H-3), 4.86–4.81 (m, 1 H, H-1), 3.84–3.80 (m, 1 H, H-5), 3.71–3.63 (m, 1 H, H-6ab), 2.32 (s, 3 H, CH3), 1.99, 1.94, 1.91 (3 s, 9 H, 3 COCH3), 1.98–1.95 (m, 1 H, H-2e), 1.79–1.72 (m, J = 12.0 Hz each, 1 H, H-2a). 13C NMR (125 MHz, CDCl3): δ = 170.3, 170.2, 169.8, 143.8–127.2 (ArC), 80.6, 72.3, 68.5, 64.9, 61.3, 31.9, 21.5, 20.8, 20.7, 20.5. ESI-MS: m/z = 466.1 [M + Na]+. Anal. Calcd for C19H25NO9S (443.12): C, 51.46; H, 5.68. Found: C, 51.32; H, 5.87. 2-Naphthyl 3,4,6-Tri-O-acetyl-2-deoxy-1-thio-α-d-galactopyranoside (19) 1H NMR (200 MHz, CDCl3): δ = 7.96–7.42 (m, 7 H, ArH), 5.91–5.88 (m, 1 H, H-1), 5.39 (br s, 1 H, H-4), 5.36–5.29 (m, 1 H, H-3), 4.74–4.70 (m, 1 H, H-5), 4.15–4.04 (m, 2 H, H-6ab), 2.58–2.47 (m, 1 H, H-2e), 2.13 (s, 3 H, COCH3), 2.11–2.07 (m, 1 H, H-2a), 2.01, 1.79 (2 s, 6 H, 2 COCH3). ESI-MS: m/z = 455.1 [M + Na]+. Anal. Calcd for C22H24O7S (432.12): C, 61.10; H, 5.59. Found: C, 61.0; H, 5.77. p-Methoxyphenyl 3,4,6-Tri-O-acetyl-2-deoxy-1-thio-α-d-galactopyranoside (20) 1H NMR (200 MHz, CDCl3): δ = 7.36–7.22 (m, 2 H, ArH), 6.79–6.75 (m, 2 H, ArH), 5.51–5.48 (m, 1 H, H-1), 5.29 (br s, 1 H, H-4), 5.24–5.14 (m, 1 H, H-3), 4.68–4.62 (m, 1 H, H-5), 4.07–4.00 (m, 2 H, H-6ab), 3.73 (s, 3 H, OCH3), 2.45–2.29 (m, 1 H, H-2e), 2.07 (s, 3 H, COCH3), 2.01–1.86 (m, 1 H, H-2a), 1.96, 1.94 (2 s, 6 H, 2 COCH3). 13C NMR (125 MHz, CDCl3): δ = 170.3, 170.1, 169.8, 159.9, 134.9 (2 C), 124.0, 114.7 (2 C), 84.7, 67.4, 66.8 (2 C), 62.4, 55.3, 30.6, 20.9, 20.0 (2 C). ESI-MS: m/z = 435.1 [M + Na]+. Anal. Calcd for C19H24O8S (412.12): C, 55.33; H, 5.87. Found: C, 55.20; H, 6.0. p-Bromophenyl 3,4,6-Tri-O-acetyl-2-deoxy-1-thio-α-d-galactopyranoside (21) 1H NMR (200 MHz, CDCl3): δ = 7.44–7.31 (m, 4 H, ArH), 5.73–5.70 (m, 1 H, H-1), 5.35 (br s, 1 H, H-4), 5.28–5.19 (m, 1 H, H-3), 4.66–4.60 (m, 1 H, H-5), 4.10–4.06 (m, 2 H, H-6ab), 2.56–2.40 (m, 1 H, H-2e), 2.14 (s, 3 H, COCH3), 2.13–2.07 (m, 1 H, H-2a), 2.00, 1.99 (2 s, 6 H, 2 COCH3). 13C NMR (125 MHz, CDCl3): δ = 170.1, 169.9, 169.6, 133.0–121.7 (ArC), 83.4, 67.7, 66.5 (2 C), 62.2, 30.5, 20.7, 20.6 (2 C). ESI-MS: m/z = 483.0 [M + Na]+. Anal. Calcd for C18H21BrO7S (460.02): C, 46.86; H, 4.59. Found: C, 46.70; H, 4.80. Benzenesulfonamido 2,3,6-Tri-deoxy-α-l-erythro-hex-2-enopyranoside (22) 1H NMR (500 MHz, CDCl3): δ = 7.87–7.40 (m, 5 H, ArH), 6.56 (d, J = 7.9 Hz, 1 H, NH), 5.79–5.76 (m, 1 H, H-2), 5.72–5.70 (m, 1 H, H-3), 5.48–5.46 (m, 1 H, H-1), 4.83–4.80 (m, 1 H, H-4), 3.33–3.29 (m, 1 H, H-5), 1.97 (s, 3 H, COCH3), 0.57 (d, J = 6.0 Hz, 3 H, CCH3). 13C NMR (125 MHz, CDCl3): δ = 170.3, 141.8–126.7 (m, ArC, C-2, C-3), 76.8, 69.9, 64.9, 20.9, 17.1. ESI-MS: m/z = 334.0 [M + Na]+. Anal. Calcd for C14H17NO5S (311.08): C, 54.01; H, 5.50. Found: C, 53.85; H, 5.69.
