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Synlett 2002(8): 1241-1244
DOI: 10.1055/s-2002-32960
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Glycosylation Driven Strategy for the Synthesis of Anomerically Pure Vinyl Sulfone-modified Pent-2-enofuranoses and Hex-2-enopyranoses

Aditya Kumar Sankia, Tanmaya Pathak*a,b
Organic Chemistry Division (Synthesis), National Chemical Laboratory, Pune 411 008, India
Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India
Fax: +91(3222)82252; e-Mail: tpathak@chem.iitkgp.ernet.in;
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Publication History

Received 1 May 2002
Publication Date:
25 July 2002 (online)

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Abstract

Both α- and β-anomers of vinyl sulfone-modified pent-2-enofuranosides have been synthesized for the first time by taking advantage of the formation of α- and β-methyl glycosides in almost equal ratio only from derivatives of d-xylose. The strategy was equally applicable in the synthesis of α- and β-anomers of vinyl sulfone-modified hex-2-enopyranosides where a d-glucose derivative was selected over a d-allose derivative as the starting material because the former almost exclusively produced the required methyl pyranosides.

Key words

modified carbohydrates - Michael acceptors - vinyl sulf­one - pent-2-enofuranoside - hex-2-enopyranoside

    References

  • 1 Collins PM. Ferrier RJ. Monosaccharides: Their Chemistry and Their Roles in Natural Products   John Wiley and Sons; Chichester: 1996.  p.189 
    Google Scholar
  • 2 Jegou E. Cleophax J. Leboul J. Gero SD. Carbohydr. Res.  1975,  45:  323 
    CrossrefGoogle Scholar
  • 3 Apostolopoulos CD. Couladouros EA. Georgiadis MP. Liebigs Ann. Chem.  1994,  781 
    Google Scholar
  • 4 Couladouros EA. Constantinou-Kokotou V. Georgiadis MP. Kokotos G. Carbohydr. Res.  1994,  254:  317 
    CrossrefGoogle Scholar
  • 5 Baer HH. Neilson T. J. Org. Chem.  1967,  32:  1068 
    Google Scholar
  • 6 Lichtenthaler FW. Vors P. Mayer N. Angew. Chem., Int. Ed. Engl.  1969,  8:  211 
    Google Scholar
  • 7 Nakagawa T. Sakakibara T. Kumazawa S. Tetrahedron Lett.  1970,  1645 
    CrossrefGoogle Scholar
  • 8 Rajabalee FJ.-M. Carbohydr. Res.  1973,  26:  219 
    CrossrefGoogle Scholar
  • 9 Paulsen H. Greve W. Chem. Ber.  1974,  107:  3013 
    Google Scholar
  • 10 Sakakibara T. Tachimori Y. Sudoh R. Tetrahedron  1984,  40:  1533 
    CrossrefGoogle Scholar
  • 11 Sakakibara T. Takai I. Yamamoto A. Tachimori Y. Sudoh R. Ishido Y. Carbohydr. Res.  1987,  169:  189 
    CrossrefGoogle Scholar
  • 12 Seta A. Tokuda K. Kaiwa M. Sakakibara T. Carbohydr. Res.  1996,  281:  129 
    CrossrefGoogle Scholar
  • 13 Bera S. Sakthivel K. Langley GJ. Pathak T. Tetrahedron  1995,  51:  7857 
    CrossrefGoogle Scholar
  • 14 Bera S. Langley GJ. Pathak T. J. Org. Chem.  1998,  63:  1754 
    CrossrefGoogle Scholar
  • 15 Simpkins NS. Sulphones in Organic Synthesis   1st Ed.:  Pergamon Press; Oxford: 1993.  p.183 
    Google Scholar
  • 16a Ravindran B. Sakthivel K. Suresh CG. Pathak T. J. Org. Chem.  2000,  65:  2637 
    Google Scholar
  • 16b Suresh CG. Ravindran B. Rao KN. Pathak T. Acta Cryst., Sect. C   2000,  C56:  1030 
    Google Scholar
  • 17a Ravindran B. Deshpande SG. Pathak T. Tetrahedron  2001,  57:  1093 
    Google Scholar
  • 17b Ravindran B. Pathak T. Ind. J. Chem. B  2001,  40:  1114 
    Google Scholar
  • 18 Yamashita A. Rosowsky A. J. Org. Chem.  1976,  41:  3422 
    Google Scholar
  • 19 Collins PM. Ferrier RJ. Monosaccharides: Their Chemistry and Their Roles in Natural Products   John Wiley and Sons; Chichester: 1996.  p.63 
    Google Scholar
  • 20 Evans ME. Angyal SJ. Carbohydr. Res.  1972,  25:  43 
    CrossrefGoogle Scholar
  • 21 Methanolysis of 1,2:5,6-di-O-isopropylidene-α-d-allofuranose in the presence of acid produced more than six products, see: Williams JM. Carbohydr. Res.  1970,  13:  281 
    CrossrefGoogle Scholar
  • 22 Nayak UG. Whistler RL. J. Org. Chem.  1969,  34:  3819 
    Google Scholar
  • 23 Peat S. Wiggins LF. J. Chem. Soc.  1938,  1088 
    Google Scholar
  • 24 Compound 19α on reaction with thiophenol produced 2-substituted d-altro-derivative, see: Hanessian S. Plessas NR. Chem. Commun.  1968,  706 
    Google Scholar
25

Analytical and spectroscopic data of selected compounds. 6α: Gummy material. Found: C, 64.48; H, 5.90; S, 8.67. C20H22O5S requires C, 64.15; H, 5.91; S, 8.56%; 1H NMR: δ = 6.59 (1 H, s), 5.88 (1 H, d, J = 4.4 Hz), 5.13 (1 H, m), 4.44 (2 H, s, PhCH2), 3.85 (1 H, dd, J = 10.7, 2.4 Hz), 3.60 (1 H, dd, J = 10.7, 4.4 Hz), 3.39 (3 H, s, OMe), 2.42 (3 H, s, ArMe). 6β: Gummy material. Found: C, 64.41; H, 6.36; S, 8.81. C20H22O5S requires C, 64.15; H, 5.91; S, 8.56%; 1H NMR: δ = 6.60 (1 H, s), 5.72 (1 H, s), 4.95 (1 H, d, J = 6.3 Hz), 4.47 (2 H, s, PhCH2), 3.83 (1 H, dd, J = 10.7, 2.4 Hz), 3.50 (1 H, m), 3.42 (3 H, s, OMe), 2.43 (3 H, s, ArMe). 16: White solid, mp 158-159 °C. Found: C, 56.19; H, 6.90; S, 8.62. C18H24O7S requires C, 56.23; H, 6.28; S, 8.34%; 1H NMR: δ = 5.96 (1 H, d, J = 3.9 Hz), 4.96 (1 H, d, J = 3.5 Hz), 1.49 (3 H, s, Me), 1.35 (3 H, s, Me), 1.29 (3 H, s, Me), 1.21 (3 H, s, Me).

26

Compounds 22α and 22β have been synthesized earlier [11] [16a] from d-glucose in 14 steps (7 steps for each anomer). The present method makes use of common intermediates upto compounds 21α and 21β, thereby drastically reducing the overall purification steps. Although overall yields for both the methods are comparable, methyl β-d-glucopyranoside, which has been used in the earlier synthesis, [11] [16a] is far too expensive a starting material to be used in a large-scale multi-step synthesis.

27

The configurations at the C-2 and C-3 positions of 23-25 have been established unambiguously. The data will be published as part of a full paper.