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Synlett 2009(16): 2633-2636  
DOI: 10.1055/s-0029-1217972
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Syntheses of Novel Sulfated Glycans for Cell-Adhesion Interaction Studies

Vipin Kumar, Robert D. Locke, Khushi L. Matta*
Cancer Biology, Roswell Park Cancer Institute, Buffalo, NY 14263, USA
Fax: +1(716)8458768; e-Mail: khushi.matta@roswellpark.org;
Further Information

Publication History

Received 23 April 2009
Publication Date:
09 September 2009 (online)

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Abstract

Stereoselective syntheses of two 3-O-Gal sulfated trisaccharides GalNAcβ(1-4)[(3-SE)-Gal]β(1-3)GalNAcα-O-All and GalNAcβ(1-4)[(3-SE)-Gal]β(1-4)Glcβ-O-All were accomplished through the use of three novel glycosyl acceptors, namely, allyl 4,6-O-benzylidene-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-α-d-galactopyranoside, methyl 2,6-di-O-benzoyl-3-O-naphthylmethyl-α-d-galactopyranoside and allyl 6-O-acetyl-2-O-benzoyl-3-O-naphthylmethyl-β-d-galactopyranosyl-(1→4)-2,3,6-tri-O-benzoyl-β-d-glucopyranoside. These sulfated trisaccharides were expected to act as potential reference compounds for human β4GalNAc transferase and can be effectively used as antigens when linked to KLH.

Key words

glycosylations - oligosaccharides - stereoselective synthesis - sulfated glycans - sulfotransferases

    References and Notes

  • 1a Breton C. Šnajdrová L. Jeanneau C. Koča J. Imberty A. Glycobiology  2006,  16:  29R 
    Google Scholar
  • 1b Paulson JC. Weinstein J. Schauer A. J. Biol. Chem.  1989,  264:  10931 
    Google Scholar
  • 2a Taniguchi N. Yoshimura M. Miyoshi E. Ihara Y. Nishikawa A. Fujii S. Glycobiology  1996,  6:  691 
    Google Scholar
  • 2b Hiraiwa N. Dohi T. Kawakami-Kimura N. Yumen M. Ohmori K. Maeda M. Kannagi R. J. Biol. Chem.  1996,  271:  31556 
    Google Scholar
  • 2c Hakomori S. Adv. Cancer Res.  1989,  52:  257 
    Google Scholar
  • 3a Ohyama C. Int. J. Clin. Oncol.  2008,  13:  308 
    Google Scholar
  • 3b Zhao Y.-Y. Takahashi M. Gu J.-G. Miyoshi E. Matsumoto A. Kitazume S. Taniguchi N. Cancer Sci.  2008,  99:  1304 ; and references cited therein
    Google Scholar
  • 4 Chandrasekaran EV. Xue J. Neelamegham S. Matta KL. Carbohydr. Res.  2006,  341:  983 
    CrossrefGoogle Scholar
  • 5a Chandrasekaran EV. Xue J. Piskorz C. Locke RD. Tóth K. Slocum HK. Matta KL. J. Cancer Res. Clin. Oncol.  2007,  133:  599 ; and references cited therein
    Google Scholar
  • 5b Chandrasekaran EV. Jain RK. Rhodes JM. Chawda R. Piskorz C. Matta KL. Glycoconjugate J.  1999,  16:  523 
    Google Scholar
  • 5c Chandrasekaran EV. Jain RK. Vig R. Matta KL. Glycobiology  1997,  7:  753 
    Google Scholar
  • 6a Campanero-Rhodes MA. Childs RA. Kiso M. Komba S. Narvor CL. Warren J. Otto D. Crocker PR. Feizi T. Biochem. Biophys. Res. Commun.  2006,  292:  1141 ; and references cited therein
    Google Scholar
  • 6b Honke K. Taniguchi N. Med. Res. Rev.  2002,  22:  637 
    Google Scholar
  • 6c Fukuda M. Hiraoka N. Akama TO. Fukuda MN. J. Biol. Chem.  2001,  276:  47747 
    Google Scholar
  • 7 Bernstein MA. Hall JD. Carbohydr. Res.  1980,  78:  C1 
    Google Scholar
  • 8 Castro-Palomino JC. Ritter G. Fortunato SR. Reinhardt S. Old LJ. Schmidt RR. Angew. Chem., Int. Ed. Engl.  1997,  36:  1998 
    CrossrefGoogle Scholar
  • 9 Sawada N. Ito M. Ishida H. Kiso M. Tetrahedron Lett.  2001,  42:  1745 
    CrossrefGoogle Scholar
  • 10 Hancock G. Galpin IJ. Tetrahedron Lett.  1982,  23:  249 
    CrossrefGoogle Scholar
  • 11 Xia J. Abbas SA. Locke RD. Piskorz CF. Alderfer JL. Matta KL. Tetrahedron Lett.  2000,  41:  169 
    CrossrefGoogle Scholar
  • 12a Sundgren A. Barchi JJ. Carbohydr. Res.  2008,  343:  1594 
    Google Scholar
  • 12b Chefalo P. Pan Y. Nagy N. Harding C. Guo Z. Glycoconjugate J.  2004,  20:  407 
    Google Scholar
  • 12c Ragupathi G. Park TK. Zhang S. Kim IJ. Graber L. Adluri S. Lloyd KO. Danishefsky SJ. Livingston PO. Angew. Chem., Int. Ed. Engl.  1997,  36:  125 
    Google Scholar
  • 13 Crich D. Vinod AU. Org. Lett.  2003,  5:  1297 
    CrossrefGoogle Scholar
  • 14 Schmidt RR. Kinzy W. Adv. Carbohydr. Chem. Biochem.  1994,  50:  21 
    PubMedGoogle Scholar
  • 15 Wang L.-X. Lee YC. J. Chem. Soc., Perkin Trans. 1  1996,  581 
    CrossrefGoogle Scholar
  • 16 Excoffier G. Gagnare D. Utille J.-P. Carbohydr. Res.  1975,  39:  368 
    CrossrefGoogle Scholar
  • 17a Komori T. Kondo S. Ando H. Ishida H. Kiso M. Carbohydr. Res.  2002,  337:  1679 
    Google Scholar
  • 17b Jain RK. Matta KL. Carbohydr. Res.  1990,  208:  51 
    Google Scholar
  • 19a Kartha KPR. Jennings HJ. J. Carbohydr. Chem.  1990,  9:  777 
    Google Scholar
  • 19b Youssef RH. Silwanis BA. El-Sokkary RI. Nematalla AS. Nashed MA. Carbohydr. Res.  1993,  240:  287 
    Google Scholar
18

Analytical Data for Compound 1
¹H NMR (400 MHz, CD3OD): δ = 1.97 (s, 3 H, NHCOCH 3), 2.03 (s, 3 H, NHCOCH 3), 3.93-3.41 (m, 16 H), 4.03-3.98 (m, 2 H), 4.11-4.09 (m, 1 H), 4.23-4.17 (m, 1 H), 4.39 (d, J = 7.6 Hz, 1 H, H-1′), 4.46-4.41 (m, 1 H), 4.63 (d, J = 8.4 Hz, 1 H, H-1′′), 5.17 (dd, ³ J = 10.4 Hz, ² J = 1.6 Hz, 1 H, OCH2CH=CH cis H trans ), 5.32 (dd, ³ J = 17.2 Hz, ² J = 1.6 Hz, 1 H, OCH2CH=CH cis H trans ), 5.99-5.89 (m, 1 H, OCH2CH=CH2) ppm. ¹³C NMR (100 MHz, CD3OD): δ = 22.9 (COCH3), 23.2 (COCH3), 55.5, 61.8, 62.8, 62.9, 69.4, 70.3, 72.4, 72.8, 72.9, 74.7, 74.8, 75.8, 77.0, 77.9, 78.5 (C-3), 78.9 (C-3′), 98.2, 104.6, 106.5 (C-1, C-1′, C-1′′), 117.8 (CH=CH2), 135.7 (CH=CH2), 174.2 (COCH3), 175.4 (COCH3) ppm. ESI-MS: m/z calcd for C25H41N2NaO19S: 728.2; found: 751.2 [M + Na]+.

20

Analytical Data for Compound 6
¹H NMR (400 MHz, CD3OD): δ = 2.06 (s, 3 H, NHCOCH 3), 3.26 (m, 1 H), 3.91-3.46 (m, 14 H), 4.16-4.01 (m, 2 H), 4.36-4.28 (m, 4 H, H-1, J = 8.0 Hz, incorporated with other protons), 4.44 (d, J = 7.6 Hz, 1 H, H-1′), 4.61 (d, J = 8.4 Hz, 1 H, H-1′′), 5.16 (dd, ³ J = 10.8 Hz, ² J = 1.2 Hz, 1 H, OCH2CH=CH cis H trans ), 5.32 (dd, ³ J = 17.6 Hz, ² J = 1.6 Hz,
1 H, OCH2CH=CH cis H trans ), 5.99-5.93 (m, 1 H, OCH2CH=CH2) ppm. ¹³C NMR (100 MHz, CD3OD): δ = 23.5 (COCH3), 54.2, 61.4, 61.9, 62.7, 69.8, 70.9, 71.3, 73.8, 74.9, 75.7, 76.4, 76.6, 76.7, 76.8, 81.0 (C-3), 81.1 (C-3′), 103.4, 104.9, 105.0 (C-1, C-1′, C-1′′), 117.6 (CH=CH2), 135.8 (CH=CH2), 174.9 (COCH3) ppm. ESI-MS: m/z calcd for C23H38NNaO19S: 687.2; found: 710.2 [M + Na]+.