Synthesis 2016; 48(08): 1177-1180
DOI: 10.1055/s-0035-1561323
paper
© Georg Thieme Verlag Stuttgart · New York

A Convenient, Gram-Scale Synthesis of 1-Deoxymannojirimycin

Fabien Stauffert
,
Mathieu L. Lepage
,
Maëva M. Pichon
,
Damien Hazelard
,
Anne Bodlenner
,
Philippe Compain*
Further Information

Publication History

Received: 18 November 2015

Accepted after revision: 15 December 2015

Publication Date:
20 January 2016 (online)


Abstract

A novel gram-scale synthesis of 1-deoxymannojirimycin from tetra-O-benzyl-d-glucopyranose in 9 steps and 28% overall yield with a limited number of purification steps is reported. The synthetic strategy is based on the regioselective deprotection and subsequent inversion of configuration of the OH group at C-2 in tetra-O-benzyl-d-glucono-δ-lactam, also an advanced intermediate toward the synthesis of 1-deoxynojirimycin derivatives.

Supporting Information

 
  • References

  • 1 Present address: Chemistry Department, UBC, 2036 Main Mall, Vancouver, BC, Canada.
  • 2 Compain P, Martin OR. Iminosugars: from Synthesis to Therapeutic Applications. Wiley-VCH; Weinheim: 2007
  • 3 Stütz AE. Iminosugars as Glycosidase Inhibitors: Nojirimycin and Beyond. Wiley-VCH; New York: 1999
  • 4 DMJ was first isolated from different legumes: Fellows LE, Bell EA, Lynn DG, Pilkiewicz F, Miura I, Nakanishi K. J. Chem. Soc., Chem. Commun. 1979; 977
  • 5 Compain P, Martin OR. Bioorg. Med. Chem. 2001; 9: 3077
    • 6a Orsato A, Barbagallo E, Costa B, Olivieri S, De Gioia L, Nicotra F, La Ferla B. Eur. J. Org. Chem. 2011; 5012
    • 6b Decroocq C, Stauffert F, Pamlard O, Oulaïdi F, Gallienne E, Martin OR, Guillou C, Compain P. Bioorg. Med. Chem. Lett. 2015; 25: 830
    • 6c Moriyama H, Tsukida T, Inoue Y, Yokota K, Yoshino K, Kondo H, Miura N, Nishimura S.-I. J. Med. Chem. 2004; 47: 1930
    • 7a Nash RJ, Kato A, Yu C.-Y, Fleet GW. J. Future Med. Chem. 2011; 3: 1513
    • 7b Horne G, Wilson FX. Prog. Med. Chem. 2011; 50: 135
    • 7c Winchester BG. Tetrahedron: Asymmetry 2009; 20: 645
  • 8 Compain P, Decroocq C, Iehl J, Holler M, Hazelard D, Mena Barragán T, Ortiz Mellet C, Nierengarten J.-F. Angew. Chem. Int. Ed. 2010; 49: 5753
    • 9a Compain P, Bodlenner A. ChemBioChem 2014; 15: 1239
    • 9b Gouin S. Chem. Eur. J. 2014; 20: 11616
    • 9c Zelli R, Longevial J.-F, Dumy P, Marra A. New J. Chem. 2015; 39: 5050
    • 9d Kanfar N, Bartolami E, Zelli R, Marra A, Winum J.-Y, Ulrich S, Dumy P. Org. Biomol. Chem. 2015; 13: 9894
  • 10 Decroocq C, Rodríguez-Lucena D, Russo V, Mena Barragán T, Ortiz Mellet C, Compain P. Chem. Eur. J. 2011; 17: 13825
  • 11 Cantarel BL, Coutinho PM, Rancurel C, Bernard T, Lombard V, Henrissat B. Nucleic Acids Res. 2009; 37: D233
    • 12a Balzarini J. FEBS Lett. 2007; 581: 2060
    • 12b Evans SV, Fellows LE, Shing TK. M, Fleet GW. J. Phytochemistry 1985; 24: 1953
  • 13 Panday N, Meyyappan M, Vasella A. Helv. Chim. Acta 2000; 83: 513
    • 14a Boucheron C, Compain P, Martin OR. Tetrahedron Lett. 2006; 47: 3081
    • 14b For a systematic study concerning the stereoselective reduction of keto sugars (hexosuloses), see: Chang C.-WT, Hui Y, Elchert B. Tetrahedron Lett. 2001; 42: 7019 ; and references cited therein
    • 15a Afarinkia K, Bahar A. Tetrahedron: Asymmetry 2005; 16: 1239
    • 15b El Ashry El Sayed H, El Nemr A. Synthesis of Naturally Occurring Nitrogen Heterocycles from Carbohydrates. Wiley-VCH; New York: 2005

      Stütz et al. have reported two multi-gram scale syntheses of DMJ from fructose or sucrose in up to 35% yields and 4 to 5 steps with minimum protecting group manipulation. The protecting group-free approach from sucrose made use of glucose isomerase, see:
    • 16a Spreitz J, Stütz AE, Wrodnigg TM. Carbohydr. Res. 2002; 337: 183
    • 16b de Raadt A, Stütz AE. Tetrahedron Lett. 1992; 33: 189
  • 17 For a large-scale synthesis of DNJ, see: Wennekes T, Lang B, Leeman M, van der Marel GA, Smits E, Weber M, van Wiltenburg J, Wolberg M, Aerts JM. F. G, Overkleeft HS. Org. Process Res. Dev. 2008; 12: 414
    • 18a Boglio C, Stahlke S, Thorimbert S, Malacria M. Org. Lett. 2005; 7: 4851
    • 18b Gandy MN, Pigott MJ, Stubbs KA. Aust. J. Chem. 2010; 63: 1409
    • 18c Concia AL, Lozano C, Castillo JA, Parella T, Joglar J, Clapés P. Chem. Eur. J. 2009; 15: 3808