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Synlett 2009(20): 3267-3270  
DOI: 10.1055/s-0029-1218361
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Efficient Stereoselective Glycosylations of Alcohols by Sugar Perpivalates: The First Use of 1-O-Pivaloylated Glycosyl Donors

Aliaksei V. Pukin, Han Zuilhof*
Laboratory of Organic Chemistry, Wageningen University, Dreijenplein 8, 6703 HB, Wageningen, The Netherlands
Fax: +31(317)484914; e-Mail: han.zuilhof@wur.nl;
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Publication History

Received 2 September 2009
Publication Date:
11 November 2009 (online)

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Abstract

1-O-Pivaloyl glycosides were shown to be efficient glycosyl donors by using the perpivaloylated derivatives of lactose, galactose and glucose in the direct ZnCl2-promoted glycosylations of various alcohols. The corresponding glycosides were isolated in good yields and β-selectivity.

Key words

carbohydrates - glycolipids - glycosyl donors - glycosylations - stereoselective synthesis

    References and Notes

  • 1 Zhu XM. Schmidt RR. Angew. Chem. Int. Ed.  2009,  48:  1900 
    CrossrefPubMedSearch in Google Scholar
  • 2a Davis BG. J. Chem. Soc., Perkin Trans. 1  2000,  2137 
  • 2b Boons GJ. Tetrahedron  1996,  52:  1095 
    Search in Google Scholar
  • 2c Toshima K. Tatsuta K. Chem. Rev.  1993,  93:  1503 
    Search in Google Scholar
  • 3a Handbook of Chemical Glycosylation: Advances in Stereoselectivity and Therapeutic Relevance   Demchenko AV. Wiley-VCH; Weinheim: 2008. 
  • 3b Smoot JT. Demchenko AV. In Advances in Carbohydrate Chemistry and Biochemistry   Vol. 62:  Elsevier Academic Press Inc; San Diego: 2009.  p.161-250  
    Search in Google Scholar
  • 3c Homann A. Seibel J. Appl. Microbiol. Biotechnol.  2009,  83:  209 
    Search in Google Scholar
  • 3d Dhanawat M. Shrivastava SK. Mini-Rev. Med. Chem.  2009,  9:  169 
    Search in Google Scholar
  • 3e Ando H. Trends Glycosci. Glycotechnol.  2008,  20:  141 
    Search in Google Scholar
  • 3f Carmona AT. Moreno-Vargas AJ. Robina I. Curr. Org. Synth.  2008,  5:  33 
    Search in Google Scholar
  • 3g Shuto S. Ichikawa S. Abe H. Matsuda A. J. Synth. Org. Chem., Jpn.  2008,  66:  50 
    Search in Google Scholar
  • 3h Castagner B. Seeberger PH. In Combinatorial Chemistry on Solid Supports   Vol. 278:  Springer-Verlag; Berlin: 2007.  p.289-309  
    Search in Google Scholar
  • 3i Galonic DP. Gin DY. Nature  2007,  446:  1000 
    Search in Google Scholar
  • 3j Toshima K. Carbohydr. Res.  2006,  341:  1282 
    Search in Google Scholar
  • 3k Demchenko AV. Kamat MN. De Meo C. Synlett  2003,  1287 
  • 3l Demchenko AV. Curr. Org. Chem.  2003,  7:  35 
    Search in Google Scholar
  • 3m Hanessian S. Lou BL. Chem. Rev.  2000,  100:  4443 
    Search in Google Scholar
  • 4a Wu D. Fujio M. Wong CH. Bioorg. Med. Chem.  2008,  16:  1073 
    Search in Google Scholar
  • 4b Huang Y. Huang JH. Xie QJ. Yao SZ. Prog. Chem.  2008,  20:  942 
    Search in Google Scholar
  • 4c Fantini J. Curr. Med. Chem.  2007,  14:  2911 
    Search in Google Scholar
  • 4d Lalazar G. Preston S. Zigrnond E. Ben Yaacov A. Ilan Y. Mini-Rev. Med. Chem.  2006,  6:  1249 
    Search in Google Scholar
  • 4e Dwek RA. Chem. Rev.  1996,  96:  683 
    Search in Google Scholar
  • 4f Varki A. Glycobiology  1993,  3:  97 
    Search in Google Scholar
  • 5a Liu Y. Palma AS. Feizi T. Biol. Chem.  2009,  390:  647 
    Search in Google Scholar
  • 5b Pieters RJ. Org. Biomol. Chem.  2009,  7:  2013 
    Search in Google Scholar
  • 5c Nan G. Yan H. Yang GL. Jian Q. Chen C. Li Z. Curr. Pharm. Biotechnol.  2009,  10:  138 
    Search in Google Scholar
  • 5d Laurent N. Voglmeir J. Flitsch SL. Chem. Commun.  2008,  4400 
  • 5e Horlacher T. Seeberger PH. Chem. Soc. Rev.  2008,  37:  1414 
    Search in Google Scholar
  • 5f Mrksich M. Chem. Soc. Rev.  2000,  29:  267 
    Search in Google Scholar
  • 5g Hernaiz MJ. de la Fuente JM. Barrientos AG. Penades S. Angew. Chem. Int. Ed.  2002,  41:  1554 
    Search in Google Scholar
  • 6a Garegg PJ. Konradsson P. Kvarnstrom I. Norberg T. Svensson SCT. Wigilius B. Acta Chem. Scand., Ser. B  1985,  39:  569 
    Search in Google Scholar
  • 6b Paulsen H. Angew. Chem., Int. Ed. Engl.  1982,  21:  155 
    Search in Google Scholar
  • 7 Schmidt RR. Kinzy W. In Advances in Carbohydrate Chemistry and Biochemistry   Vol. 50:  Academic Press Inc; San Diego: 1994.  p.21 
    Search in Google Scholar
  • 8a Codee JDC. Litjens R. van den Bos LJ. Overkleeft HS. van der Marel GA. Chem. Soc. Rev.  2005,  34:  769 
    Search in Google Scholar
  • 8b Garegg PJ. In Advances in Carbohydrate Chemistry and Biochemistry   Vol. 52:  Academic Press Inc; San Diego: 1997.  p.179 
    Search in Google Scholar
  • 8c Fugedi P. Garegg PJ. Lonn H. Norberg T. Glycoconjugate J.  1987,  4:  97 
    Search in Google Scholar
  • 9 Toshima K. Carbohydr. Res.  2000,  327:  15 
    CrossrefSearch in Google Scholar
  • 10 Trincone A. Giordano A. Curr. Org. Chem.  2006,  10:  1163 
    CrossrefSearch in Google Scholar
  • 11 Meloncelli PJ. Martin AD. Lowary TL. Carbohydr. Res.  2009,  344:  1110 
    CrossrefSearch in Google Scholar
  • 12a Morales-Serna JA. Boutureira O. Diaz Y. Matheu MI. Castillon S. Carbohydr. Res.  2007,  1595 
  • 12b Morales-Serna JA. Boutureira O. Diaz Y. Matheu MI. Castillon S. Org. Biomol. Chem.  2008,  6:  443 
    Search in Google Scholar
  • 13a Gouin SG. Pilgrim W. Porter RK. Murphy PV. Carbohydr. Res.  2005,  340:  1547 
    Search in Google Scholar
  • 13b Milkereit G. Gerber S. Brandenburg K. Morr M. Vill V. Chem. Phys. Lipids  2005,  135:  1 
    Search in Google Scholar
  • 13c Katsuraya K. Ikushima N. Takahashi N. Shoji T. Nakashima H. Yamamoto N. Yoshida T. Uryu T. Carbohydr. Res.  1994,  260:  51 
    Search in Google Scholar
  • 13d Dahmen J. Frejd T. Gronberg G. Lave T. Magnusson G. Noori G. Carbohydr. Res.  1983,  116:  303 
    Search in Google Scholar
  • 13e Banoub J. Bundle DR. Can. J. Chem.-Rev. Can. Chim.  1979,  57:  2085 
    Search in Google Scholar
  • 13f Hanessian S. Banoub J. Carbohydr. Res.  1977,  59:  261 
    Search in Google Scholar
  • 14 Murakami T. Hirono R. Sato Y. Furusawa K. Carbohydr. Res.  2007,  342:  1009 
    CrossrefSearch in Google Scholar
  • 15a Seebacher W. Haslinger E. Weis R. Monatsh. Chem.  2001,  132:  839 
    Search in Google Scholar
  • 15b Magnus V. Vikictopic D. Iskric S. Kveder S. Carbohydr. Res.  1983,  114:  209 
    Search in Google Scholar
  • 15c Wulff G. Schmidt W. Carbohydr. Res.  1977,  53:  33 
    Search in Google Scholar
  • 16a Murakami T. Sato Y. Shibakami M. Carbohydr. Res.  2008,  343:  1297 
    Search in Google Scholar
  • 16b Yao QJ. Song J. Xia CF. Zhang WP. Wang PG. Org. Lett.  2006,  8:  911 
    Search in Google Scholar
  • 16c Rai AN. Basu A. J. Org. Chem.  2005,  70:  8228 
    Search in Google Scholar
  • 16d Takeda Y. Horito S. Carbohydr. Res.  2005,  340:  211 
    Search in Google Scholar
  • 16e Yamamura T. Hada N. Kaburaki A. Yamano K. Takeda T. Carbohydr. Res.  2004,  339:  2749 
    Search in Google Scholar
  • 16f Compostella F. Franchini L. De Libero G. Palmisano G. Ronchetti F. Panza L. Tetrahedron  2002,  58:  8703 
    Search in Google Scholar
  • 16g Lindberg J. Svensson SCT. Pahlsson P. Konradsson P. Tetrahedron  2002,  58:  5109 
    Search in Google Scholar
  • 16h Gege C. Geyer A. Schmidt RR. Chem. Eur. J.  2002,  8:  2454 
    Search in Google Scholar
  • 16i Castro-Palomino JC. Simon B. Speer O. Leist M. Schmidt RR. Chem. Eur. J.  2001,  7:  2178 
    Search in Google Scholar
  • 16j Nicolaou KC. Li J. Zenke G. Helv. Chim. Acta  2000,  83:  1977 
    Search in Google Scholar
  • 17 Presser A. Kunert O. Potschger I. Monatsh. Chem.  2006,  137:  365 
    CrossrefSearch in Google Scholar
  • 18a Pukin AV. Weijers C. van Lagen B. Wechselberger R. Sun B. Gilbert M. Karwaski MF. Florack DEA. Jacobs BC. Tio-Gillen AP. van Belkum A. Endtz HP. Visser GM. Zuilhof H. Carbohydr. Res.  2008,  343:  636 
    Search in Google Scholar
  • 18b Sun B. Pukin AV. Visser GM. Zuilhof H. Tetrahedron Lett.  2006,  47:  7371 
    Search in Google Scholar
  • 18c de Smet L. Pukin AV. Stork GA. de Vos CHR. Visser GM. Zuilhof H. Sudholter EJR. Carbohydr. Res.  2004,  339:  2599 
    Search in Google Scholar
  • 19a de Smet L. Pukin AV. Sun QY. Eves BJ. Lopinski GP. Visser GM. Zuilhof H. Sudholter EJR. Appl. Surf. Sci.  2005,  252:  24 
    Search in Google Scholar
  • 19b de Smet LCPM. Stork GA. Hurenkarnp GHF. Sun QY. Topal H. Vronen PJE. Sieval AB. Wright A. Visser GM. Zuilhof H. Sudholter EJR. J. Am. Chem. Soc.  2003,  125:  13916 
    Search in Google Scholar
  • 20a Sisu C. Baron AJ. Branderhorst HM. Connel SD. Weijers C. de Vries R. Hayes ED. Pukin AV.
    Gilbert     M. Pieters RJ. Zuilhof H. Visser GM. Turnbull WB. ChemBioChem  2009,  10:  329 
    Search in Google Scholar
  • 20b Pukin AV. Branderhorst HM. Sisu C. Weijers C. Gilbert M. Liskamp RMJ. Visser GM. Zuilhof H. Pieters RJ. ChemBioChem  2007,  8:  1500 
    Search in Google Scholar
  • 21 Barrientos AG. de la Fuente JM. Rojas TC. Fernandez A. Penades S. Chem. Eur. J.  2003,  9:  1909 
    CrossrefSearch in Google Scholar
  • 24a Lemieux RU. Can. J. Chem.-Rev. Can. Chim.  1951,  29:  1079 
    Search in Google Scholar
  • 24b Lemieux RU. Brice C. Can. J. Chem.-Rev. Can. Chim.  1955,  33:  109 
    Search in Google Scholar
22

Data for 2b: ¹H NMR (400 MHz, C6D6): δ = 6.52 (d, J = 3.8 Hz, 1 H), 5.82 (t, J = 9.8 Hz, 1 H), 5.28 (t, J = 9.9 Hz, 1 H), 5.23 (dd, J = 10.0, 3.8 Hz, 1 H), 4.21-4.28 (m, 2 H), 4.08-4.14 (m, 1 H), 1.16 (s, 9 H), 1.12 (s, 9 H), 1.12 (s, 9 H), 1.09 (s, 9 H), 1.08 (s, 9 H); ¹³C NMR (100 MHz, C6D6): δ = 177.8, 177.2, 176.9, 176.8, 175.9, 89.5, 71.4, 70.5, 70.3, 68.5, 62.4, 39.4, 39.3, 39.2 (2 C, peaks overlap), 39.1, 27.7, 27.6, 27.5, 27.5, 27.4.

23

Typical glycosylation procedure: To a solution of lactose octapivalate 1 (1 g, 0.99 mmol) and 8-chlorooctan-1-ol (4b; 243 µL, 1.48 mmol) in anhydrous toluene (10 mL), was added ZnCl2 (0.2 g, 1.48 mmol, which was dried in vacuo at 120 ˚C for at least 1 h prior to use) and the resulting suspension was stirred at 70 ˚C for 5 h. After cooling, the reaction mixture was diluted with EtOAc (10 mL), and solid NaHCO3 (2 g) and H2O (0.5 mL) were added portion-wise with stirring. After the formation of gas stopped (˜20 min), the solution was filtered over Hyflo. The precipitate was washed thoroughly with EtOAc. The combined organic phase was evaporated in vacuo and the residue was purified by silica gel column chromatography (EtOAc-petroleum ether, 1:7) to give 8-chlorooctyl lactoside 5b (0.97 g, 0.9 mmol, 91%) as a white foam. ¹H NMR (400 MHz, CDCl3): δ = 5.36 (d, J = 2.3 Hz, 1 H), 5.18 (t, J = 9.5 Hz, 1 H), 5.09 (dd, J = 10.5, 8.0 Hz, 1 H), 4.96 (dd, J = 10.5, 3.5 Hz, 1 H), 4.79 (dd, J = 9.7, 7.9 Hz, 1 H), 4.50 (d, J = 7.8 Hz, 1 H), 4.47-4.56 (m, 1 H), 4.44 (d, J = 8.0 Hz, 1 H), 4.18 (dd, J = 12.0, 5.0 Hz, 1 H), 4.04-4.11 (m, 1 H), 3.95-4.03 (m, 1 H), 3.88-3.94 (m, 1 H), 3.85 (t, J = 9.5 Hz, 1 H), 3.67-3.75 (m, 1 H), 3.47 (t, J = 6.8 Hz, 2 H), 3.44-3.53 (m, 1 H), 3.33-3.41 (m, 1 H), 1.65-1.75 (m, 2 H), 1.48 (t, J = 6.4 Hz, 2 H), 1.32-1.42 (m, 2 H), 1.22-1.28 (m, 6 H), 1.21 (s, 9 H), 1.19 (s, 9 H), 1.17 (s, 9 H), 1.15 (s, 9 H), 1.11 (s, 9 H), 1.11 (s, 9 H), 1.05 (s, 9 H); ¹³C NMR (101 MHz, CDCl3): δ = 177.7, 177.5, 177.2, 177.0, 176.7, 176.5, 175.9, 100.7, 100.0, 73.7, 73.3, 71.7, 71.6, 71.4, 71.3, 69.6, 68.8, 66.8, 61.7, 61.3, 44.9, 38.9-38.6 (7 C, peaks overlap), 32.5, 29.4, 29.0, 28.7, 27.3, 27.2, 27.1, 27.0 (3 C, peaks overlap), 26.9, 26.7, 25.8.