Synlett 2015; 26(04): 421-425
DOI: 10.1055/s-0034-1379979
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© Georg Thieme Verlag Stuttgart · New York

Unprotected Carbohydrates as Starting Material in Chemical Synthesis: Not Just a Challenge but an Opportunity

Tiina Saloranta*
Laboratory of Organic Chemistry, Åbo Akademi University, Piispankatu 8, 20500 Turku, Finland   Email: tiina.saloranta@abo.fi
,
Reko Leino
Laboratory of Organic Chemistry, Åbo Akademi University, Piispankatu 8, 20500 Turku, Finland   Email: tiina.saloranta@abo.fi
› Author Affiliations
Further Information

Publication History

Received: 28 November 2014

Accepted after revision: 17 December 2014

Publication Date:
03 February 2015 (online)


Abstract

Development of reaction sequences that utilize renewable resources, such as carbohydrates, as starting material is of topical interest. Particularly attractive are reaction protocols where unprotected mono- and oligosaccharides are applied. Herein, selected approaches for direct derivatization of unprotected carbohydrates are highlighted. Ultimately, such methodologies are also applicable for natural polysaccharides resulting in rapid development of novel functional biobased materials for future applications.

1 Introduction

2 Reacting Unprotected Carbohydrates as Aldehydes

3 Approaches for Selective Reactions Targeting the Nonanomeric Hydroxyl Groups on Unprotected Carbohydrates

4 Protecting-Group-Free Synthesis of Glycoclusters and Glycoconjugates

5 Conclusions

 
  • References

  • 1 For a review on protecting-group-free synthesis, see: Young IS, Baran PS. Nat. Chem. 2009; 1: 193
  • 2 Carbohydrates . Osborn HM. I. Elsevier Science; Oxford: 2003
  • 3 For a review, see: Hsu C.-H, Hung S.-C, Wu C.-Y, Wong C.-H. Angew. Chem. Int. Ed. 2011; 50: 11872
  • 4 For the exact compositions of the tautomeric mixtures for aldohexoses determined by studying the equilibrium of 13C-labeled compounds by 13C NMR spectroscopy, see: Zhu Y, Zajicek J, Serianni AS. J. Org. Chem. 2001; 66: 6244
  • 5 For a comprehensive review on methods for shortening and lengthening the carbon chain in carbohydrates, see: Monrad RN, Madsen R. Tetrahedron 2011; 67: 8825
    • 6a Kiliani H. Ber. Dtsch. Chem. Ges. 1886; 19: 767
    • 6b Fischer E. J. Am. Chem. Soc. 1890; 12: 461
    • 7a Lundt I, Madsen R. Synthesis 1995; 787
    • 7b Hotchkiss D, Soengas R, Simone MI, van Ameijde J, Hunter S, Cowley AR, Fleet GW. J. Tetrahedron Lett. 2004; 45: 9461
    • 7c Soengas R, Izumori K, Simone MI, Watkin DJ, Skytte UP, Soetaert W, Fleet GW. J. Tetrahedron Lett. 2005; 46: 5755
    • 8a Railton CJ, Clive DL. J. Carbohydr. Res. 1996; 218: 69
    • 8b Jørgensen M, Iversen EH, Madsen R. J. Org. Chem. 2001; 66: 4625
  • 9 van Kalkeren HA, van Rootselaar S, Haasjes FS, Rutjes FP. J. T, van Delft FL. Carbohydr. Res. 2012; 362: 30
  • 10 Ranoux A, Lemiègre L, Benoit M, Guégan J.-P, Benvegnu T. Eur. J. Org. Chem. 2010; 1314
  • 11 Schmid W, Whitesides GM. J. Am. Chem. Soc. 1991; 113: 6674
  • 12 Kim E, Gordon DM, Schmid W, Whitesides GM. J. Org. Chem. 1993; 58: 5500
  • 13 Gordon DM, Whitesides GM. J. Org. Chem. 1993; 58: 7937
  • 14 Palmelund A, Madsen R. J. Org. Chem. 2005; 70: 8248
  • 15 Saloranta T, Müller C, Vogt D, Leino R. Chem. Eur. J. 2008; 14: 10539
  • 16 For a review, see: Boucard V, Broustal G, Campagne JM. Eur. J. Org. Chem. 2007; 225
    • 17a Voigt B, Scheffler U, Mahrwald R. Chem. Commun. 2012; 48: 5304
    • 17b Voigt B, Matviitsuk A, Mahrwald R. Tetrahedron 2013; 69: 4302
    • 18a Pfaffe M, Mahrwald R. Org. Lett. 2012; 14: 792
    • 18b Schmalisch S, Mahrwald R. Org. Lett. 2013; 15: 5854
    • 18c Matviitsuk A, Berndt F, Mahrwald R. Org. Lett. 2014; 16: 5474
  • 19 Rodrigues F, Canac Y, Lubineau A. Chem. Commun. 2000; 2049
  • 20 Rai VK, Singh S, Singh P, Yadav LD. S. Synthesis 2010; 4051
  • 21 Nourisefat M, Panahi F, Khalafi-Nezhad A. Org. Biomol. Chem. 2014; 12: 9419
  • 22 Lee D, Taylor MS. Synthesis 2012; 44: 3421
  • 23 Davis NJ, Flitsch SL. Tetrahedron Lett. 1993; 34: 1181
  • 24 Breton T, Bashiardes G, Léger J.-M, Kokoh KB. Eur. J. Org. Chem. 2007; 1567
  • 25 For a review, see: Bragd PL, van Bekkum H, Besemer AC. Top. Catal. 2004; 27: 49
  • 26 Freimund S, Huwig A, Giffhorn F, Köpper S. Chem. Eur. J. 1998; 4: 2442
  • 27 Jäger M, Hartmann M, de Vries JG, Minnaard AJ. Angew. Chem. Int. Ed. 2013; 52: 7809

    • See, for example:
    • 28a Farnandez-Megia E, Correa J, Rodríguez-Meizoso I, Riguera R. Macromolecules 2006; 39: 2113
    • 28b Ladmiral V, Mantovani G, Clarkson GJ, Cauet S, Irwin JL, Haddleton DM. J. Am. Chem. Soc. 2006; 128: 4823
    • 29a Gouin SG, Kovensky J. Tetrahedron Lett. 2007; 48: 2875
    • 29b Besset C, Chambert S, Fenet B, Queneau Y. Tetrahedron Lett. 2009; 50: 7043
  • 30 See, for example: Negishi K, Mashiko Y, Yamashita E, Otsuka A, Hasegawa T. Polymers 2011; 3: 489
  • 31 Tanaka T, Nagai H, Noguchi M, Kobayashi A, Shoda S.-i. Chem. Commun. 2009; 3378
  • 32 Lim D, Brimble MA, Kowalczyk R, Watson AJ. A, Fairbanks AJ. Angew. Chem. Int. Ed. 2014; 53: 11907
  • 33 Kimura Y, Ito S, Shimizu Y, Kanai M. Org. Lett. 2013; 15: 4130
  • 34 Cho C.-C, Liu J.-N, Chien C.-H, Shie J.-J, Chen Y.-C, Fang J.-M. J. Org. Chem. 2009; 74: 1549