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Synlett 2013; 24(5): 581-586
DOI: 10.1055/s-0032-1318406
letter
© Georg Thieme Verlag Stuttgart · New York

Nitrosyl Tetrafluoroborate Catalyzed Preparation of 2,3-Unsaturated Glycosides and 2-Deoxyglycosides of Hindered Alcohols, Thiols, and Sulfonamides

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
› Author Affiliations
Further Information

Publication History

Received: 25 January 2013

Accepted: 17 February 2013

Publication Date:
01 March 2013 (online)

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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

glycal - Ferrier rearrangement - NOBF4 - 2,3-unsaturated glycoside - 2-deoxyglycoside
 

  • References and Notes

  • 1 Danishefsky SJ, Bilodeau MT. Angew. Chem., Int. Ed. Engl. 1996; 35: 1380
    CrossrefSearch in Google Scholar
  • 2 Fraser-Reid B. Acc. Chem. Res. 1985; 18: 347
    CrossrefSearch in Google Scholar
  • 3 Holder NL. Chem. Rev. 1982; 82: 287
    CrossrefSearch in Google Scholar
  • 4 Ferrier RJ. Topics Curr. Chem. 2001; 215: 153
    Search in Google Scholar
  • 5 Liu ZJ, Zhou M, Min JM, Zhang LH. Tetrahedron: Asymmetry 1999; 10: 2119
    CrossrefSearch in Google Scholar
  • 6 Bussolo VD, Kim YJ, Gin DY. J. Am. Chem. Soc. 1998; 120: 13515
    CrossrefSearch in Google Scholar
  • 7 Remers WA In The Chemistry of Antitumor Antibiotics . Wiley-Interscience; New York: 1979: 133-175
    Search in Google Scholar
  • 8 Toshima K, Tatsuda K. Chem. Rev. 1993; 93: 1503
    CrossrefSearch in Google Scholar
  • 9 Matsumoto K, Ebata T, Matsushita H. Carbohydr. Res. 1995; 267: 187
    CrossrefSearch in Google Scholar
  • 10 Fakha G, Sinou D. Molecules 2005; 10: 859
    CrossrefSearch in Google Scholar
  • 11 Tiwari P, Misra AK. J. Org. Chem. 2006; 71: 2911
    CrossrefSearch in Google Scholar
  • 12 Cardona F, Valenza S, Picasso S, Goti A, Brandi A. J. Org. Chem. 1998; 63: 7311
    CrossrefSearch in Google Scholar
  • 13 Klaffke W, Pudlo P, Springer D, Thiem J. Liebigs Ann. Chem. 1991; 6: 509
    Search in Google Scholar
  • 14 Bhate P, Horton D, Priebe W. Carbohydr. Res. 1985; 144: 331
    CrossrefSearch in Google Scholar
  • 15 Toshima K, Ishizuka T, Matsuo G, Nakata M. Chem. Lett. 1993; 2013
  • 16 Babu BS, Balasubramanian KK. Tetrahedron Lett. 2000; 41: 1271
    CrossrefSearch in Google Scholar
  • 17 Koreeda M, Houston TA, Shull BK, Klemke E, Tuinman RJ. Synlett 1995; 90
    Thieme Connect
  • 18 Takhi M, Abdel-Rahman AA.-H, Schmidt RR. Tetrahedron Lett. 2001; 42: 4053
    CrossrefSearch in Google Scholar
  • 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
    CrossrefSearch in Google Scholar
  • 21 Hou D, Lowary TL. Carbohydr. Res. 2009; 344: 1911 ; and references cited therein
    CrossrefSearch in Google Scholar
  • 22 Yadav JS, Reddy BV. S, Reddy KB, Satyanarayana M. Tetrahedron Lett. 2002; 43: 7009
    CrossrefSearch in Google Scholar
  • 23 Chandrasekhar S, Reddy CR, Chandrashekar G. Tetrahedron Lett. 2004; 45: 6481
    CrossrefSearch in Google Scholar
  • 24 Colinas PA, Bravo RD. Carbohydr. Res. 2007; 342: 2297
    CrossrefSearch in Google Scholar
  • 25 Témpera CA, Colinas PA, Bravo RD. Tetrahedron Lett. 2010; 51: 5372
    CrossrefSearch in Google Scholar
  • 26 Ding F, William R, Gorityala BK, Ma J, Wang S, Liu XW. Tetrahedron Lett. 2010; 51: 3146
    CrossrefSearch in Google Scholar
  • 27 Rodríguez OM, Colinas PA, Bravo RD. Synlett 2009; 1154
    Thieme Connect
  • 28 Misra AK, Tiwari P, Agnihotri G. Synthesis 2005; 260
    Thieme Connect
  • 29 Levecque P, Gammon DW, Jacobs P, De Vos D, Sels B. Green Chem. 2010; 12: 828
    CrossrefSearch in Google Scholar
  • 30 Das SK, Reddy KA, Roy J. Synlett 2003; 1607
    Thieme Connect
  • 31 Sau A, Santra A, Misra AK. Synlett 2012; 23: 2341
    Thieme ConnectSearch in Google Scholar
  • 32 Priebe W, Zamojski A. Tetrahedron 1980; 36: 287
    CrossrefSearch in Google Scholar
  • 33 Dunkerton LV, Adair NK, Euske JM, Brady KT, Robinson PD. J. Org. Chem. 1988; 53: 845
    CrossrefSearch in Google Scholar
  • 34 Jordan MA, Wilson L. Nat. Rev. Cancer 2004; 4: 253
    CrossrefPubMedSearch in Google Scholar
  • 35 Supuran CT. Exp. Opin. Invest. Drugs 2003; 12: 283
    CrossrefSearch in Google Scholar
  • 36 Ferrier RJ, Zubkov OA. Org. React. 2003; 62: 569
    Search in Google Scholar
  • 37 Colinas PA, Bravo RD. Org. Lett. 2003; 5: 4509
    CrossrefSearch in Google Scholar
  • 38 Tilve RD, Alexander MV, Khandekar AC, Samant SD, Kanetkar VR. J. Mol. Catal. A: Chem. 2004; 223: 237
    CrossrefSearch in Google Scholar
  • 39 Bettadaiah BK, Srinivas P. Tetrahedron Lett. 2003; 44: 7257
    CrossrefSearch in Google Scholar
  • 40 Guchhait G, Misra AK. Catal. Lett. 2011; 141: 925
    CrossrefSearch in Google Scholar
  • 41 Brown DS, Ley SV, Vile S, Thompson M. Tetrahedron 1991; 47: 1329
    CrossrefSearch in Google Scholar
  • 42 Reddy BV. S, Divyavani C, Yadav JS. Synthesis 2010; 1617
    Thieme Connect
  • 43 Grynkiewicz G, Priebe W, Zamojski A. Carbohydr. Res. 1979; 68: 33
    CrossrefSearch in Google Scholar
  • 44 Banaszek A, Zamojski A. Polish J. Chem. 1979; 53: 2029
    Search in Google Scholar
  • 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.