Download PDF
Synthesis 2017; 49(16): 3686-3691
DOI: 10.1055/s-0036-1589501
paper
© Georg Thieme Verlag Stuttgart · New York

Facile Approaches to 2-Deoxy-d-glucose and 2-Deoxy-α-d-glucopyranonucleosides from d-Glucal

Wenke Xu
a   School of Pharmaceutical Sciences, Zhengzhou Universit, P. R. of China   Email: fwliu@zzu.edu.cn
,
Hui Yang
a   School of Pharmaceutical Sciences, Zhengzhou Universit, P. R. of China   Email: fwliu@zzu.edu.cn
,
Yingju Liu
a   School of Pharmaceutical Sciences, Zhengzhou Universit, P. R. of China   Email: fwliu@zzu.edu.cn
,
Yingchun Hua
a   School of Pharmaceutical Sciences, Zhengzhou Universit, P. R. of China   Email: fwliu@zzu.edu.cn
,
Bin He
a   School of Pharmaceutical Sciences, Zhengzhou Universit, P. R. of China   Email: fwliu@zzu.edu.cn
,
Xin Ning
a   School of Pharmaceutical Sciences, Zhengzhou Universit, P. R. of China   Email: fwliu@zzu.edu.cn
,
Zhiyan Qin
a   School of Pharmaceutical Sciences, Zhengzhou Universit, P. R. of China   Email: fwliu@zzu.edu.cn
,
Hong-Min Liu
a   School of Pharmaceutical Sciences, Zhengzhou Universit, P. R. of China   Email: fwliu@zzu.edu.cn
b   Collaborative Innovation Center of Henan New Drug Research and Safety Evaluation, P. R. of China
,
Feng-Wu Liu*
a   School of Pharmaceutical Sciences, Zhengzhou Universit, P. R. of China   Email: fwliu@zzu.edu.cn
b   Collaborative Innovation Center of Henan New Drug Research and Safety Evaluation, P. R. of China
› Author AffiliationsFinancial support from National Natural Science Foundation of China (21372207) is gratefully acknowledged.
Further Information

Publication History

Received: 20 April 2017

Accepted after revision: 24 April 2017

Publication Date:
07 June 2017 (online)

    Permissions and Reprints All articles of this category


Abstract

Convenient and stereoselective methods for the preparation of 2-deoxy-d-glucose and purine 2-deoxy-α-d-glucopyranonucleosides were developed. Halogen-mediated O-glycosidation of d-glucal by bromine in MeOH followed by reductive removal of the halo group and hydrolysis of methoxy group by zinc in saturated aqueous sodium dihydrogen phosphate gave 2-deoxy-d-glucose. Treatment of 3,4,6-tri-O-acetyl-d-glucal with IBr and 2,6-dichloropurine based on haloetherification and subsequent reductive removal of iodine and deprotection allowed the isolation of purin-9-yl 2-deoxy-α-d-glucopyranonucleoside. Preparation of several purin-9-yl 2-deoxy-α-d-glucopyranoside derivatives is also reported. Their configuration was confirmed by single crystal X-ray analysis of the key intermediate 2,6-dichloro-9-(2-iodo-2-deoxy-α-d-glucopyranosyl)purine.

Key words

glucal - 2-deoxy-d-glucose - 2-deoxy-α-d-glucopyranonucleoside - halogen-mediated O-glycosidation - stereoselective synthesis

Supporting Information

    Supporting information for this article is available online at https://doi.org /10.1055/s-0036-1589501.
  • Supporting Information
 

  • References

    • 1a Sabesan S. Neira S. J. Org. Chem. 1991; 56: 5468
      Crossref
    • 1b Yadav JS. Reddy BV. S. Bhaskar Reddy K. Satyanarayana M. Tetrahedron Lett. 2002; 43: 7009
      Crossref
  • 3 Christopher LF. Richard WF. J. Org. Chem. 1999; 64: 1424
    Crossref
  • 4 Danishefsky SJ. Bilodeau MT. Angew. Chem., Int. Ed. Engl. 1996; 35: 1380
    Crossref
  • 5 Marzabadi CH. Dios A. Geer A. Franck RW. J. Org. Chem. 1998; 63: 6673
    Crossref

      • For example:
    • 6a Miller JN. Pongdee R. Tetrahedron Lett. 2013; 54: 3185
      Crossref
    • 6b Zhao J. Wei S. Ma X. Shao H. Carbohydr. Res. 2010; 345: 168
      CrossrefPubMed
    • 6c Nord LD. Dalley NK. McKernan PA. Robins RK. J. Med. Chem. 1987; 30: 1044
      CrossrefPubMed
    • 6d Gervay J. Danishefsky S. J. Org. Chem. 1991; 56: 5448
      Crossref
    • 6e Marzabadi CH. Franck RW. Tetrahedron 2000; 56: 8385
      Crossref
  • 7 Ciment DM. Ferrier RJ. J. Chem. Soc. C 1966; 441
    Crossref
  • 8 Bolitt V. Mioskowski C. Lee S.-G. Falck JR. J. Org. Chem. 1990; 55: 5812
    Crossref
  • 9 Cui X.-K. Zhong M. Meng X.-B. Li Z.-J. Carbohydr. Res. 2012; 358: 19
    CrossrefPubMed
  • 10 Durham TB. Roush WR. Org. Lett. 2003; 5: 1875
    CrossrefPubMed
  • 11 Sirion U. Purintawarrakun S. Sahakitpichan P. Saeeng R. Carbohydr. Res. 2010; 345: 2401
    CrossrefPubMed
  • 12 Liu F. Liu Y. Xu R.-G. Dai G. Zhao L.-X. Wang Y. Liu H.-M. Liu F.-W. Pannecouque C. Herdewijn P. Chemistry & Biodiversity 2015; 12: 813
    CrossrefPubMed
  • 13 Fischer E. Zach K. Sitzungsber. Kl. Preuss. Akad. Wiss. 1913; 27: 311
  • 14 Forbes CL. Frank RW. J. Org. Chem. 1999; 64: 1424
    Crossref
  • 15 Kovacs G. Toth K. Dinya Z. Somsak L. Micskei K. Tetrahedron 1999; 55: 5253
    Crossref
  • 16 Spencer RP. Schwartz J. Tetrahedron 2000; 56: 2103
    Crossref
  • 17 Binch H. Stangier K. Thiem J. Carbohydr. Res. 1998; 306: 409
    Crossref
  • 18 Meyerhoefer TJ. Kershaw S. Caliendo N. Eltayeb S. Hanawa-Romero E. Bykovskaya P. Huang V. Marzabadi CH. De Castro M. Eur. J. Org. Chem. 2015; 2457