Download PDF
Synlett 2009(7): 1141-1143  
DOI: 10.1055/s-0028-1088147
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Nonchiral-Pool Synthesis of (+)-Hyacinthacine B1

Paidi Venkatram Reddy, Peter Koos, Amaël Veyron, Andrew E. Greene, Philippe Delair*
Département de Chimie Moléculaire (SERCO) UMR-5250, ICMG FR-2607, CNRS Université Joseph Fourier, B. P. 53, 38041 Grenoble Cedex 9, France
Fax: +33(4)76635754; e-Mail: philippe.delair@ujf-grenoble.fr;
Further Information

Publication History

Received 18 November 2008
Publication Date:
20 March 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

The first nonchiral-pool total synthesis of (+)-hyacinthacine B1 has been achieved. The synthesis uses as key steps an efficient [2+2] cycloaddition of dichloroketene to a chiral enol ether, two diastereoselective Bruylants-like alkylations, and an effective double Tamao-Fleming oxidation.

Key words

stereoselective synthesis - natural products - azasugars - cycloadditions - double Tamao-Fleming oxidation

    References and Notes

  • 1 Iminosugars   Compain P. Martin OR. John Wiley and Sons; Chichester: 2007. 
    Google Scholar
  • 2a Asano N. Nash RJ. Molyneux RJ. Fleet GWJ. Tetrahedron: Asymmetry  2000,  11:  1645 
    Google Scholar
  • 2b Butters TD. Dwek RA. Platt FM. Chem. Rev.  2000,  100:  4683 
    Google Scholar
  • 2c Robina I. Moreno-Vargas AJ. Carmona AT. Vogel P. Curr. Drug Metab.  2004,  5:  329 
    Google Scholar
  • 2d Borges de Melo E. da Silva Gomes A. Carvalho I. Tetrahedron  2006,  62:  10277 
    Google Scholar
  • 2e Gerber-Lemaire S. Juillerat-Jeanneret L. Mini Rev. Med. Chem.  2006,  6:  1043 
    Google Scholar
  • For a review on polyhydroxylated pyrrolizidines, see:
  • 3a Yoda H. Curr. Org. Chem.  2002,  6:  223 
    Google Scholar
  • For a review on pyrrolizidines, see:
  • 3b Liddell JR. Nat. Prod. Rep.  2002,  19:  773 
    Google Scholar
  • 3c Liddell JR. Nat. Prod. Rep.  2001,  18:  441 
    Google Scholar
  • 3d Liddell JR. Nat. Prod. Rep.  2000,  17:  455 
    Google Scholar
  • 3e Liddell JR. Nat. Prod. Rep.  1999,  16:  499 
    Google Scholar
  • 3f Liddell JR. Nat. Prod. Rep.  1998,  15:  363 
    Google Scholar
  • 3g Nash RJ. Watson AA. Asano N. In Alkaloids: Chemical & Biological Per-spectives   Vol. 11:  Pelletier SW. Elsevier Science; Oxford: 1996.  p.345 
    Google Scholar
  • 4 See: Kato A. Kato N. Adachi I. Hollinshead J. Fleet GW. Kuriyama C. Ikeda K. Asano N. Nash RJ.
    J. Nat. Prod.  2007,  70:  993 ; and references cited therein
    CrossrefGoogle Scholar
  • For recent examples, see:
  • 5a Chabaud L. Landais Y. Renaud P. Org. Lett.  2005,  7:  2587 
    Google Scholar
  • 5b Desvergenes S. Py S. Vallée Y. J. Org. Chem.  2005,  70:  1459 
    Google Scholar
  • 5c Donohoe TJ. Sintim HO. Hollinshead J. J. Org. Chem.  2005,  70:  7297 
    Google Scholar
  • 5d Dewi-Wülfing P. Blechert S. Eur. J. Org. Chem.  2006,  1852 
    Google Scholar
  • 5e Donohoe TJ. Thomas RE. Chem. Rec.  2007,  7:  180 
    Google Scholar
  • 5f Zhou L. Chen J. Cao X.-P. Synthesis  2007,  1359 
    Google Scholar
  • 5g Izquierdo I. Plaza MT. Tamayo JA. Sanchez-Cantalejo F. Eur. J. Org. Chem.  2007,  6078 
    Google Scholar
  • 5h Izquierdo I. Plaza MT. Tamayo JA. Yanez V. Lo Re D. Sanchez-Cantalejo F. Tetrahedron  2008,  64:  4613 
    Google Scholar
  • 5i Donohoe TJ. Thomas RE. Cheeseman MD. Rigby CL. Bhalay G. Linney ID. Org. Lett.  2008,  10:  3615 
    Google Scholar
  • 5j Chandrasekhar S. Parida BB. Rambabu C. J. Org. Chem.  2008,  73:  7826 
    Google Scholar
  • 5k For asymmetric syntheses of related compounds, see: Denmark SE. Martinborough EA. J. Am. Chem. Soc.  1999,  121:  3046  (australine)
    Google Scholar
  • 5l Trost BM. Aponick A. Stanzl BN. Chem. Eur. J.  2007,  13:  9547 (australine) 
    Google Scholar
  • 5m Denmark SE. Hurd AR. J. Org. Chem.  2000,  65:  2875 (casuarine) 
    Google Scholar
  • 6 Reddy PV. Veyron A. Koos P. Bayle A. Greene AE. Delair P. Org. Biomol. Chem.  2008,  6:  1170 
    CrossrefGoogle Scholar
  • 7 Greene AE. Charbonnier F. Tetrahedron Lett.  1985,  26:  5525 
    CrossrefGoogle Scholar
  • Pyrrolidines:
  • 8a Kanazawa A. Gillet S. Delair P. Greene AE. J. Org. Chem.  1998,  63:  4660 
    Google Scholar
  • 8b Delair P. Brot E. Kanazawa A. Greene AE. J. Org. Chem.  1999,  64:  1383 
    Google Scholar
  • 8c Ceccon J. Poisson J.-F. Greene AE. Synlett  2005,  1413 
    Google Scholar
  • Indolizidines:
  • 9a Pourashraf M. Delair P. Rasmussen M. Greene AE. J. Org. Chem.  2000,  65:  6966 
    Google Scholar
  • 9b Rasmussen M. Delair P. Greene AE. J. Org. Chem.  2001,  66:  5438 
    Google Scholar
  • 9c Ceccon J. Poisson J.-F. Greene AE. Org. Lett.  2006,  8:  4739 
    Google Scholar
  • Pyrrolizidines:
  • 10a Roche C. Delair P. Greene AE. Org. Lett.  2003,  5:  1741 
    Google Scholar
  • 10b Roche C. Kadlecíková K. Veyron A. Delair P. Philouze C. Greene AE. Flot D. Burghammer M. J. Org. Chem.  2005,  70:  8352 
    Google Scholar
  • 11 Kato A. Adachi I. Miyauchi M. Ikeda K. Komae T. Kizu H. Kameda Y. Watson AA. Nash RJ. Wormald MR. Fleet GWJ. Asano N. Carbohydr. Res.  1999,  316:  95 
    CrossrefGoogle Scholar
  • 12 To the best of our knowledge, only a very recent synthesis of hyacinthacine B1 starting from l-pyroglutamic acid has been published prior to this report. See: Sengoku T. Satoh Y. Oshima M. Takahashi M. Yoda H. Tetrahedron  2008,  64:  8052 
    CrossrefGoogle Scholar
  • 15a Bruylants P. Bull. Soc. Chim. Belg.  1924,  33:  467 
    Google Scholar
  • For mechanistic studies, see:
  • 15b Beaufort-Droal V. Pereira E. Théry V. Aitken DJ. Tetrahedron  2006,  62:  11948 
    Google Scholar
  • 15c Aitken DJ. Beaufort V. Chalard P. Cladière JL. Dufour M. Pereira E. Théry V. Tetrahedron  2002,  58:  5933 
    Google Scholar
  • For a review, see:
  • 16a Enders D. Shilvock JP. Chem. Soc. Rev.  2000,  29:  359 
    Google Scholar
  • See also:
  • 16b Husson HP. Royer J. Chem. Soc. Rev.  1999,  28:  383 
    Google Scholar
  • 17a Durand J.-O. Larchevêque M. Petit Y. Tetrahedron Lett.  1998,  39:  5743 
    Google Scholar
  • 17b Matsubara R. Kawai N. Kobayashi S. Angew. Chem. Int. Ed.  2006,  45:  3814 
    Google Scholar
  • 18a Xia Q. Ganem B. Tetrahedron. Lett.  2002,  43:  1597 
    Google Scholar
  • 18b White JM. Tunoori AR. Georg GI. J. Am. Chem. Soc.  2000,  122:  11995 
    Google Scholar
  • 19 Kim S. Ahn KH. J. Org. Chem.  1984,  49:  1717 
    CrossrefGoogle Scholar
  • 20 For a review, see: Jones GR. Landais Y. Tetrahedron  1996,  52:  7599 
    CrossrefGoogle Scholar
  • See, for example:
  • 21a Smitrovich JH. Woerpel KA. J. Org. Chem.  1996,  61:  6044 
    Google Scholar
  • 21b Molander GA. Nichols PJ. J. Org. Chem.  1996,  61:  6040 
    Google Scholar
  • 21c Overman LO. Wild H. Tetrahedron Lett.  1989,  30:  647 
    Google Scholar
  • 21d Polniaszek RP. Dillard LW. J. Org. Chem.  1992,  57:  4103 
    Google Scholar
  • See also ref. 22g
  • 22a Fleming I. Ghosh SK. J. Chem. Soc., Chem. Commun.  1992,  1775 
    Google Scholar
  • 22b Chen RM. Weng WW. Luh TY.
    J. Org. Chem.  1995,  60:  3272 
    Google Scholar
  • 22c Shimada T. Mukaide K. Shinohara A. Han JW. Hayashi T. J. Am. Chem. Soc.  2002,  124:  1584 
    Google Scholar
  • 22d Berry MB. Griffiths RJ. Sanganee MJ. Steel PG. Whelligan DK. Tetrahedron Lett.  2003,  44:  9135 
    Google Scholar
  • 22e Landais Y. Mahieux C. Tetrahedron Lett.  2005,  46:  675 
    Google Scholar
  • 22f Restorp P. Fischer A. Somfai P. J. Am. Chem. Soc.  2006,  128:  12646 
    Google Scholar
  • 22g Dressel M. Restorp P. Somfai P. Chem. Eur. J.  2008,  14:  3072 ; and references cited therein
    Google Scholar
13

Both (R)- and (S)-Stericol® are now available from Sigma-Aldrich. (S)-Stericol® was chosen on the basis of previous work [8-¹0] that indicated it would lead to natural hyacinthacine B1.

14

The lactam was obtained as a 93:7 (¹H NMR) mixture of diastereomers. The minor enantiomer filtered out over the remainder of the synthesis.

23

The corresponding tetraacetates were also found to be identical by chromatography (TLC) in several different solvent systems and by ¹H and ¹³C NMR.