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Synlett 2009(8): 1269-1272  
DOI: 10.1055/s-0029-1216733
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Total Synthesis of the Epimer at C-6′ of the Miharamycin B Framework

Filipa Marceloa,c, Robert Abou-Jneida, Matthieu Sollogouba, Jérôme Marrotb, Amélia P. Rauter*c, Yves Blériot*a
a Institut Parisien de Chimie Moléculaire, UMR 7201, Equipe Glycochimie, UPMC Univ. Paris 06, 4 Place Jussieu, 75005 Paris, France
Fax: +33(1)44275504; e-Mail: yves.bleriot@upmc.fr;
b Institut Lavoisier, Université de Versailles-Saint-Quentin, UMR 8180, 78035 Versailles, France
c Carbohydrate Chemistry Group, CQB-FCUL, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade de Lisboa, 1749-016 Lisbon, Portugal
Fax: +351(21)7500088; e-Mail: aprauter@fc.ul.pt;
Further Information

Publication History

Received 30 December 2008
Publication Date:
17 April 2009 (online)

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Abstract

The total synthesis of the epimer at C-6′ of the core of the complex nucleoside antibiotic miharamycin B is reported. Opti­mization of the N-glycosylation key step involving the atypical 2-aminopurine nucleobase and a bicyclic glycosyl donor enabled to access the N 9-nucleoside in reasonable yield which was further decorated. The stereochemistry at C-6′ has been secured by X-ray crystallography.

Key words

antibiotics - natural products - nucleosides - total synthesis

    References and Notes

  • 1a Knapp S. Chem. Rev.  1995,  95:  1859 ; and references cited herein
    Google Scholar
  • 1b Garner P. In Studies in Natural Product Chemistry   Vol. 1:  . Elsevier; Amsterdam: 1988.  p.397-434  
    Google Scholar
  • 2 Ichikawa S. Matsuda A. Exp. Opin. Ther. Pat.  2007,  17:  487 
    CrossrefGoogle Scholar
  • 3a Goto T. Toya Y. Ohgi T. Kondo T. Tetrahedron Lett.  1982,  23:  1271 
    Google Scholar
  • 3b Hara K. Fujimoto H. Sato KI. Hashimoto H. Yoshimura J. Carbohydr. Res.  1987,  159:  65 
    Google Scholar
  • 3c Rauter AP. Fernandes AC. Czernecki S. Valery J.-M. J. Org. Chem.  1996,  61:  3594 
    Google Scholar
  • 3d Czernecki S. Franco S. Valery J.-M. J. Org. Chem.  1997,  62:  4845 
    Google Scholar
  • 3e Xue J. Guo Z. J. Carbohydr. Chem.  2008,  27:  51 
    Google Scholar
  • 4 For some recent syntheses, see: Ichikawa S. Matsuda A. Nucleosides, Nucleotides Nucleic Acids  2005,  24:  319 
    CrossrefGoogle Scholar
  • 5 Marcelo F. Jiménez-Barbero J. Marrot J. Rauter AP. Sinaÿ P. Blériot Y. Chem. Eur. J.  2008,  14:  10066 
    CrossrefPubMedGoogle Scholar
  • 6a Tsuruoka T. Yumoto H. Ezaki N. Niida T. Sci. Reports of Meiji Seika Kasha  1967,  9:  1 
    Google Scholar
  • 6b Noguchi T. Yasuda Y. Niida T. Shomura T. Ann. Phytopath. Soc. Japan  1968,  34:  323 
    Google Scholar
  • 7a For synthetic efforts towards the northern moiety of miharamycins, see: Czernecki S. Franco S. Horns S. Valery J.-M. Tetrahedron Lett.  1996,  37:  4003 
    Google Scholar
  • 7b For synthetic efforts towards the southern moiety of miharamycins, see: Garner P. Yoo JU. Saraku R. Tetrahedron  1992,  48:  4259 
    Google Scholar
  • 8 Seto H. Koyama M. Ogino H. Tsuruoka T. Inouye S. Otake N. Tetrahedron Lett.  1983,  24:  1805 
    CrossrefGoogle Scholar
  • 10a Edmonds DJ. Johnston D. Procter DJ. Chem. Rev.  2004,  104:  3371 
    Google Scholar
  • 10b Blériot Y. Untersteller E. Fritz B. Sinaÿ P. Chem. Eur. J.  2002,  8:  240 
    Google Scholar
  • 11 Fairbanks AJ. Sinaÿ P. Synlett  1995,  277 
    Article in Thieme ConnectGoogle Scholar
  • 16 Jensen HH. Nordstrom LU. Bols M. J. Am. Chem. Soc.  2004,  126:  9205 
    CrossrefPubMedGoogle Scholar
  • 17 Angibeaud P. Utille J.-P. J. Chem. Soc., Perkin Trans. 1  1990,  5:  1490 
    Google Scholar
  • 18 Corrie JET. J. Chem. Soc., Perkin Trans. 1  1993,  18:  2161 
    Google Scholar
  • 19 Vorbrüggen H. Hofle G. Chem. Ber.  1981,  114:  1256 
    CrossrefGoogle Scholar
  • 20 Koshkin AA. J. Org. Chem.  2004,  69:  3711 
    CrossrefGoogle Scholar
  • 21 The lack of reactivity of 2-aminopurine has been reported by other groups, see: Stauffer CS. Datta A. J. Org. Chem.  2008,  73:  4166 
    CrossrefGoogle Scholar
  • 22 Robins MJ. Zou R. Gou Z. Wnuk SF. J. Org. Chem.  1996,  61:  9207 
    CrossrefGoogle Scholar
  • 23 Jetten M. Peters AM. Van Nispen JWFM. Ottenheijm HCJ. Tetrahedron Lett.  1991,  32:  6025 
    CrossrefGoogle Scholar
  • 24 Vaughan JR. J. Am. Chem. Soc.  1951,  73:  3547 
    Google Scholar
9

Marcelo F., Silva, F. V. M.; Goulart, M.; Justino, J.; Blériot, Y.; Rauter, A. P. in preparation.

12

CCDC 716056 contains the supplementary crystallographic data for this structure. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.ac.uk/data _request/cif.

13

Hydroxy esters 5 and 5′ were difficult to separate and therefore were used as a mixture.

14

CCDC 716057 contains the supplementary crystallographic data for this structure. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.ac.uk/data _request/cif.

15

CCDC 695608 contains the supplementary crystallographic data for this structure. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.ac.uk/data _request/cif.