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Synthesis 2010(5): 749-756  
DOI: 10.1055/s-0029-1218628
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Highly Stereoselective Synthesis of 2-Amino-3-C-methyl-2,3-dideoxyaldoses by C3-Chain Elongation via Homoaldol Reaction of Sugar Aldehydes

Sabine Kollmann, Roland Fröhlich, Dieter Hoppe*
Westfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstrasse 40, 48149 Münster, Germany
Fax: +49(251)8336531; e-Mail: dhoppe@uni-muenster.de;
Further Information

Publication History

Received 11 September 2009
Publication Date:
04 January 2010 (online)

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Abstract

A flexible strategy for the stereoselective synthesis of branched amino sugar analogues is described. It is based on a C3-chain elongation of suitable protected aldoses. By using the sequence homoaldol reaction, epoxidation, and methanolysis α-methyl allo-furanosides are obtained. Proximate amination of the corresponding triflates afford the title compounds. All reactions proceed with high yield, high diastereoselectivities, and allow for a broad application.

Key words

homoaldol reaction - stereoselective synthesis - furanosides - aminoaldoses - carbamates

    References

  • 2a Tang P. Mamdani F. Hu X. Liu JO. Yu B. Bioorg. Med. Chem. Lett.  2007,  17:  1003 
    Google Scholar
  • 2b Ferrier RJ. Carbohydr. Chem.  2003,  34:  166 
    Google Scholar
  • 2c Gravier-Pelletier C. Milla M. Le Merrer Y. Depezay J.-C. Eur. J. Org. Chem.  2001,  3089 
    Google Scholar
  • Selected examples:
  • 3a Zhang C. Fu Q. Albermann C. Li L. Thorson JS. ChemBioChem  2007,  8:  385 
    Google Scholar
  • 3b Hanessian S. Kloss J. Tetrahedron Lett.  1985,  26:  1261 
    Google Scholar
  • 3c Sarabia F. Martin-Ortiz L. Lopez-Herrera FJ. Org. Lett.  2003,  5:  3927 
    Google Scholar
  • Selected examples:
  • 4a Anizon F. Belin L. Moreau P. Sancelme M. Voldoire A. Prudhomme M. Ollier M. Sevère D. Riou J.-F. Bailly C. Fabbro D. Meyer T. J. Med. Chem.  1997,  40:  3456 
    Google Scholar
  • 4b El-Hamamsy MHRI. Smith AW. Thompson AS. Threadgill MD. Bioorg. Med. Chem.  2007,  15:  4552 
    Google Scholar
  • Selected examples:
  • 5a Zhang C. Griffith BR. Fu Q. Albermann C. Fu X. Lee I.-K. Li L. Thorson JS. Science  2006,  313:  1291 
    Google Scholar
  • 5b Ahmed SA. Odde S. Daga PR. Bowling JJ. Mesbah MK. Youssef DT. Khalifa SI. Doerksen RJ. Hamann MT. Org. Lett.  2007,  9:  4773 
    Google Scholar
  • 6a Pfrengle F. Lentz D. Reißig H.-U. Angew. Chem. Int. Ed.  2009,  48:  3165 ; Angew. Chem 2009, 121, 3211
    Google Scholar
  • 6b Ferrier RJ. Carbohydr. Chem.  2003,  34:  175 
    Google Scholar
  • 6c Ferrier RJ. Carbohydr. Chem.  2003,  34:  118 
    Google Scholar
  • 6d Nicolaou KC. Chem JS. Edmonds RJ. Estrada AA. Angew. Chem. Int. Ed.  2009,  48:  660 ; Angew. Chem. 2009, 121, 670
    Google Scholar
  • 6e Westermann B. Neuhaus C. Angew. Chem. Int. Ed.  2005,  46:  4077 ; Angew. Chem. 2005, 117, 4145
    Google Scholar
  • 6f Enders D. Grondal G. Vretton M. Raabe G. Angew. Chem. Int. Ed.  2005,  44:  4079 ; Angew. Chem. 2005, 117, 4147
    Google Scholar
  • 8 Hoppe D. Hanko R. Brönneke A. Lichtenberg F. van Hülsen E. Chem. Ber.  1985,  118:  2822 
    CrossrefGoogle Scholar
  • For reviews, see:
  • 9a Hoppe D. Hense T. Angew. Chem., Int. Ed. Engl.  1997,  36:  2282 ; Angew. Chem. 1997, 109, 2376
    Google Scholar
  • 9b Hoppe D. Marr F. Brüggemann M. Top. Organomet. Chem.  2003,  5:  61 
    Google Scholar
  • 9c Christoph G. Hoppe D. In The Chemistry of Organolithium Compounds   Rappoport Z. Marek I. Wiley; Chichester: 2004.  p.1055 
    Google Scholar
  • 9d Hoppe D. Synthesis  2009,  43 
    Google Scholar
  • 10a Hoppe D. Zschage O. Angew. Chem. Int. Ed.  1989,  26:  69 ; Angew. Chem. 1989, 101, 67
    Google Scholar
  • 10b Paulsen H. Graeve C. Hoppe D. Synthesis  1996,  141 
    Google Scholar
  • 11a Tipson RS. Cohen A. Carbohydr. Res.  1968,  7:  232 
    Google Scholar
  • 11b Jackson DY. Synth. Commun.  1988,  18:  337 
    Google Scholar
  • 11c Schmidt OT. Methods Carbohydr. Chem.  1963,  2:  318 
    Google Scholar
  • 11d Czernecki S. Dieulesaint A. Valery J.-M. J. Carbohydr. Chem.  1986,  5:  469 
    Google Scholar
  • 11e Szarek MA. Wu X. Szarek WA. Carbohydr. Res.  1997,  299:  165 
    Google Scholar
  • 11f Swern D. J. Org. Chem.  1978,  43:  2480 
    Google Scholar
  • 11g Redlich H. Kölln O. Synthesis  1995,  1376 
    Google Scholar
  • 11h Leonard NJ. Carraway KL. J. Heterocycl. Chem.  1966,  3:  485 
    Google Scholar
  • 11i Fernandes RA. Eur. J. Org. Chem.  2007,  5064 ; and references cited therein
    Google Scholar
  • 12 Kollmann S. Fröhlich R. Hoppe D. Synthesis  2007,  883 
    Article in Thieme ConnectGoogle Scholar
  • 13a Hoppe D. Lüßmann J. Jones PG. Schmidt D. Sheldrick GM. Tetrahedron Lett.  1986,  27:  3591 
    Google Scholar
  • 13b Sharpless KB. Verhoeven T. Aldrichimica Acta  1979,  12:  63 
    Google Scholar
  • 13c Wang Z. Schreiber SL. Tetrahedron Lett.  1990,  31:  31 
    Google Scholar
  • 13d Torres G. Torres W. Prieto JA. Tetrahedron  2004,  60:  10245 
    Google Scholar
  • 13e Ohshima T. Chem. Pharm. Bull.  2004,  52:  1031 
    Google Scholar
  • For reviews see:
  • 13f Sharpless KB. Angew. Chem. Int. Ed.  2002,  41:  2024 ; Angew. Chem. 2002, 114, 2126
    Google Scholar
  • 13g Sharpless KB. Johnson RA. In Catalytic Asymmetric Synthesis   2nd ed.:  Ojima I. Wiley-VCH; Weinheim: 2000.  p.231 
    Google Scholar
  • 13h Marco-Contelles I. Molina MT. Anjum S. Chem. Rev.  2004,  104:  2857 
    Google Scholar
  • 13i Katsuki T. Curr. Org. Chem.  2001,  5:  663 
    Google Scholar
  • 14 Hoppe D. Tarara G. Wilckens M. Synthesis  1989,  83 
    Article in Thieme ConnectGoogle Scholar
  • 15 Ünaldi S. Fröhlich R. Hoppe D. Synthesis  2005,  2507 
    Article in Thieme ConnectGoogle Scholar
  • 18 COLLECT   Nonius B. V.; Delft: 1998. 
    Google Scholar
  • 19 Otwinowski Z. Minor W. Methods in Enzymology: Macromolecular Crystallography, Part A   276:  Carter CW. Sweet RM. Academic Press; New York: 1997.  p.307-326  
    Google Scholar
  • 20 Otwinowski Z. Borek D. Majewski W. Minor W. Acta Crystallogr., Sect. A  2003,  59:  228 
    CrossrefPubMedGoogle Scholar
  • 21 Sheldrick GM. Acta Crystallogr., Sect. A  1990,  46:  467 
    CrossrefGoogle Scholar
  • 22 Sheldrick GM. Acta Crystallogr., Sect. A  2008,  64:  112 
    CrossrefPubMedGoogle Scholar
  • 23 Brüggemann M. Mopict   Universität Münster; Münster: 2001. 
    Google Scholar
  • 25a Binkley RM. Ambrose MG. J. Carbohydr. Res.  1984,  3:  1 
    Google Scholar
  • 25b Review: Stang PJ. Hanack M. Subramanian LR. Synthesis  1982,  85 
    Google Scholar
  • 26a Fuchs W. Voelter W. Liebigs Ann. Chem.  1982,  1920 
    Google Scholar
  • 26b Hanessian S. Preparative Carbohydrate Chemistry   Marcel Decker; New York: 1997. 
    Google Scholar
  • 27a Corey EJ. Nicolaou KC. Balanson RD. Machida Y. Synthesis  1975,  590 
    Google Scholar
  • 27b Reddy PG. Pratap TV. Kumar GDK. Mohanty SK. Baskaran S. Eur. J. Org. Chem.  2002,  3740 
    Google Scholar
  • 28 Dearden MJ. Firkin CR. Hermet J.-P. O’Brien P. J. Am. Chem. Soc.  2002,  124:  11870 
    CrossrefGoogle Scholar
1

X-ray crystal structure analysis.

7

A research in Scifinder afforded no hit.

16

X-ray crystal structure analysis of 7c: Formula C17H28O8, M = 360.39, colorless crystal 0.30 × 0.20 × 0.10 mm, a = 10.0328(3), b = 9.4646(3), c = 10.1594(3) Å, β = 106.772(2)˚, V = 923.66(5) ų, ρcalc = 1.296 g cm-³, µ = 0.861 mm-¹, empirical absorption correction (0.782 ≤ T ≤ 0.919), Z = 2, monoclinic, space group P21 (No. 4), λ = 1.54178 Å, T = 223 K, ω and φ scans, 5102 reflections collected ± h, ± k, ± l), [(sin θ)/λ] = 0.60 Å-¹, 2615 independent (R int = 0.030) and 2563 observed reflections [I ≥ 2 σ (I)], 233 refined parameters, R = 0.034, wR ² = 0.089, Flack parameter -0.10 (19), max. residual electron density 0.14 (-0.18) e Å-³, hydrogen atoms calculated and refined as riding atoms.

17

Data set was collected with a Nonius KappaCCD diffractometer. Programs used: data collection COLLECT,¹8 data reduction Denzo-SMN,¹9 absorption correction Denzo,²0 structure solution SHELXS-97,²¹ structure refinement SHELXL-97,²² and graphics Mopict.²³

24

CCDC 747428 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033, E-mail: deposit@ccdc.cam.ac.uk].