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Synthesis 2011(8): 1290-1294  
DOI: 10.1055/s-0030-1258475
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Novel Concise Synthesis of (±)-Noviose and l-(+)-Noviose by Palladium-Catalyzed Epoxide Opening

Yoshitaka Matsushima*, Jun Kino
Department of Chemistry, Hamamatsu University School of Medicine, Handayama, Hamamatsu 431-3192, Japan
Fax: +81(53)4352319; e-Mail: ymatsu@hama-med.ac.jp;
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Publikationsverlauf

Received 28 December 2010
Publikationsdatum:
14. März 2011 (online)

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Abstract

We established a novel, concise synthetic route for obtaining noviose, the deoxy sugar component of aminocoumarin antibiotics. l-(+)-Noviose was successfully synthesized by utilizing a palladium-catalyzed epoxide-opening reaction and the subsequent lactone formation as key reactions, starting from a nonsugar chiral epoxide, which is easily available in both enantiomeric forms.

Key words

noviose - novobiocin - aminocoumarin antibiotics - palladium-catalyzed epoxide opening

    References

  • 1 Weymouth-Wilson AC. Nat. Prod. Rep.  1997,  14:  99 
    CrossrefSuche in Google Scholar
  • 2 Paloma LG. Smith JA. Chazin WJ. Nicolaou KC. J. Am. Chem. Soc.  1994,  116:  3697 
    CrossrefSuche in Google Scholar
  • 3 Nedal A. Zotchev SB. Appl. Microbiol. Biotechnol.  2004,  64:  7 
    CrossrefSuche in Google Scholar
  • 4 Matsushima Y. Kino J. Tetrahedron Lett.  2005,  46:  8609 
    CrossrefSuche in Google Scholar
  • 5 Matsushima Y. Kino J. Tetrahedron Lett.  2006,  47:  8777 
    CrossrefSuche in Google Scholar
  • 6 Matsushima Y. Kino J. Tetrahedron  2008,  64:  3943 
    CrossrefSuche in Google Scholar
  • 7 Matsushima Y. Kino J. Eur. J. Org. Chem.  2010,  2206 
  • 8 For the latest review on novobiocin related aminocoumarins, see: Heide L. Biotechnol. Adv.  2009,  27:  1006 
    CrossrefSuche in Google Scholar
  • 9 García IG. Stevenson CEM. Usón I. Meyers CFL. Walsh CT. Lawson DM. J. Mol. Biol.  2010,  395:  390 
    CrossrefSuche in Google Scholar
  • 10 Donnelly A. Blagg BSJ. Cur. Med. Chem.  2008,  15:  2702 
    CrossrefSuche in Google Scholar
  • 11a Vaterlaus BP. Kiss J. Spiegelberg H. Helv. Chim. Acta  1964,  47:  381 
    Suche in Google Scholar
  • 11b Kiss J. Spiegelberg H. Helv. Chim. Acta  1964,  47:  398 
    Suche in Google Scholar
  • 11c Klemer A. Waldmann M. Liebigs Ann. Chem.  1986,  221 
  • 11d Laurin P. Ferroud D. Klich M. Dupuis-Hamelin C. Mauvais P. Lassaigne P. Bonnefoy A. Musicki B. Bioorg. Med. Chem. Lett.  1999,  9:  2079 
    Suche in Google Scholar
  • 11e Periers A.-M. Laurin P. Benedetti Y. Lachaud S. Ferroud D. Iltis A. Haesslein J.-L. Klich M. L’Hermite G. Musicki B. Tetrahedron Lett.  2000,  41:  867 
    Suche in Google Scholar
  • 11f Takeuchi M. Taniguchi T. Ogasawara K. Tetrahedron Lett.  2000,  41:  2609 
    Suche in Google Scholar
  • 11g Gammon DW. Hunter R. Wilson S. Tetrahedron Lett.  2002,  43:  3141 
    Suche in Google Scholar
  • 11h Ješelnik M. Leban I. Polanc S. Kočevar M. Org. Lett.  2003,  5:  2651 
    Suche in Google Scholar
  • 11i Hanessian S. Auzzas L. Org. Lett.  2008,  10:  261 
    Suche in Google Scholar
  • 11j He Y. Xue J. Zhou Y. Yang J. Yu X. Tetrahedron Lett.  2009,  50:  2317 ; this is the latest paper, however, l-(+)-noviose was reported as a by-product during the synthesis of noviose 1,2-acetonide by the modified route given in references 11d and 11e
    Suche in Google Scholar
  • 12a Pankau WM. Kreiser W. Helv. Chim. Acta  1998,  81:  1997 
    Suche in Google Scholar
  • 12b Pankau WM. Kreiser W. Tetrahedron Lett.  1998,  39:  2089 
    Suche in Google Scholar
  • 12c Yu XM. Shen G. Blagg BSJ.
    J. Org. Chem.  2004,  69:  7375 
    Suche in Google Scholar
  • 12d Reddy DS. Srinivas G. Rajesh BM. Kannan M. Rajale TV. Iqbal J. Tetrahedron Lett.  2006,  47:  6373 
    Suche in Google Scholar
  • 13 Donnelly A. Zhao H. Kusuma BR. Blagg BSJ. Med. Chem. Commun.  2010,  1:  165 
    CrossrefSuche in Google Scholar
  • 14 During our course of pursuing the effective synthesis of osmundalactones, an appealing method for the δ-lactoniza-tion accompanied by trans-cis isomerization was reported: Ono M. Zhao XY. Shida Y. Akita H. Tetrahedron  2007,  63:  10140 
    CrossrefSuche in Google Scholar
  • 15 Yu X.-Q. Yoshimura F. Ito F. Sasaki M. Hirai A. Tanino K. Miyashita M. Angew. Chem. Int. Ed.  2008,  47:  750 
    CrossrefSuche in Google Scholar
  • 16a Starting chiral epoxide (-)-7b was prepared from 3-methylbut-2-en-1-ol in 3 steps according to the literature: Krief A. Dumont W. Baillieul D. Synthesis  2002,  2019 
  • 16b

    (-)-7b: [α]D ²6.9 -33.2 (c 1.05, CHCl3) {Lit.¹6 [α]D ²0 -30.64 (c 1.155, CHCl3)}; IR (neat): 2954, 1724, 1657, 1437, 1379, 1319, 1296, 1263, 1173, 980, 804 cm-¹; ¹H NMR (270 MHz, CDCl3): δ = 6.84 (dd, J = 6.5, 15.7 Hz, 1 H), 6.12 (dd, J = 1.1, 15.6 Hz, 1 H), 3.76 (s, 3 H), 3.33 (dd, J = 0.9, 6.4 Hz, 1 H), 1.41 (s, 3 H), 1.29 (s, 3 H); ¹³C NMR (67.8 MHz, CDCl3): δ = 166.1, 143.1, 124.4, 62.1, 61.7, 51.7, 24.6, 18.6

  • 17a Starting diene 8 was prepared according to the literature: Balu N. Thomas JV. Bhat SV. J. Med. Chem.  1991,  34:  2821 
    Suche in Google Scholar
  • 17b

    See also: ref. 19

  • 17c

    8: IR (neat): 2981, 2933, 1711, 1639, 1612, 1446, 1367, 1308, 1277, 1213, 1161, 1140, 1039, 991, 879 cm-¹; ¹H NMR (270 MHz, CDCl3): δ = 7.56 (dd, J = 11.5, 15.2 Hz, 1 H), 5.99 (br dq, J = 1.1, 11.7 Hz, 1 H), 5.76 (d, J = 15.2 Hz, 1 H), 4.20 (q, J = 7.1 Hz, 2 H), 1.89 (d, J = 0.9 Hz, 3 H), 1.88 (s, 3 H), 1.30 (t, J = 7.1 Hz, 3 H); ¹³C NMR (67.8 MHz, CDCl3): δ = 167.7, 146.2, 141.0, 123.7, 118.6, 60.1, 26.5, 18.9, 14.3

  • 18 Marschall H. Penninger J. Weyerstahl P. Liebigs Ann. Chem.  1982,   49 
  • 19 Uchida K. Ishigami K. Watanabe H. Kitahara T. Tetrahedron  2007,  63:  1281 
    CrossrefSuche in Google Scholar
  • 21 Nagumo S. Nakano T. Hata K. Mizukami M. Miyashita M. Org. Lett.  2010,  12:  908 
    CrossrefSuche in Google Scholar
  • 22a Achmatowicz O. Grynkiewicz G. Szechner B. Tetrahedron  1976,  32:  1051 
    Suche in Google Scholar
  • 22b

    This article was occasionally quoted as the reference for the synthesis of (±)-noviose by mistake, which, however, certainly includes ¹H NMR data of synthesized methyl dl-novioside along with those of naturally derived noviose.

20

Acid-catalyzed epoxide opening of (±)-7a (cat. H2SO4-MeOH or BF3˙OEt2-MeOH) resulted in a ratio of approximately 1:4 to 1:6 (desired/undesired), which was roughly estimated by ¹H NMR analysis of the crude products.