Skip to main content
SpringerLink
Log in

Thio-click approach to the synthesis of stable glycomimetics

  • Original Paper
  • Published:
Chemical Papers Aims and scope Submit manuscript

Abstract

Carbon-sulfur-bridged glycomimetics were prepared by free radical hydrothiolation of the exocyclic double bond of unsaturated sugars. Reaction between benzoyl-substituted pyranoid-exoglycal and a range of thiols including peptide, 1-thioglycerol and 1-thiosugar derivatives gave β-D-configured carbon-sulfur-linked glycoconjugates with full stereoselectivity. Addition of a panel of thiols to a 3-exomethylene-glucofuranose derivative also proceeded in a stereoselective manner and afforded a series of D-allo-configured 3-deoxy-3-C-S-bridged glycoconjugates.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Acton, E. M., Goerner, R. N., Uh, H. S., Ryan, K.J., Henry, D. W., Cass, C. E., & LePage, G. A. (1979) Improved antitumor effects in 3′-branched homologs of 2′-deoxythioguanine. Synthesis and evaluation of thioguanine nucleosides of 2,3-dideoxy-3-(hydroxymethyl)-D-erythro-pentofuranose. Journal of Medicinal Chemistry, 22, 518–525.DOI: 10.1021/jm00191a012.

    Article  CAS  Google Scholar 

  • Chakka, N., Johnston, B. D., & Pinto, B. M. (2005) Synthesis and conformational analysis of disaccharide analogues containing disulfide and selenosulfide functionalities in the interglycosidic linkages. Canadian Journal of Chemistry, 83, 929–936.DOI: 10.1139/v05-107.

    Article  CAS  Google Scholar 

  • Dénès, F., Pichowicz, M., Povie, G., & Renaud, P. (2014) Thiyl radicals in organic synthesis. Chemical Reviews, 114, 2587–2693.DOI: 10.1021/cr400441m.

    Article  Google Scholar 

  • Dondoni, A., & Marra, A. (2012) Recent applications of thiolene coupling as a click process for glycoconjugation. Chemical Society Reviews, 41, 573–586.DOI: 10.1039/c1cs15157f.

    Article  CAS  Google Scholar 

  • Ernst, B., & Magnani, J. L. (2009) From carbohydrate leads to glycomimetic drugs. Nature Reviews Drug Discovery, 8, 661–677.DOI: 10.1038/nrd2852.

    Article  CAS  Google Scholar 

  • Fiore, M., Marra, A., & Dondoni, A. (2009) Photoinduced thiol-ene coupling as a click ligation tool for thiodisaccharide synthesis. Journal of Organic Chemistry, 74, 4422–4425.DOI: 10.1021/jo900514w.

    Article  CAS  Google Scholar 

  • Illyés, T. Z., Szabó, T., & Szilágyi, L. (2011) Glycosylation via mixed disulfide formation using glycosylthio-phthalimides and -succinimides as glycosylsulfenyl-transfer reagents. Carbohydrate Research, 346, 1622–1627.DOI: 10.1016/j.carres.2011.04.020.

    Article  Google Scholar 

  • Lázár, L., Csávás, M., Herczeg, M., Herczegh, P., & Borbás, A. (2012) Synthesis of S-linked glycoconjugates and S-disaccharides by thiol-ene coupling reaction of enoses. Organic Letters, 14, 4650–4653.DOI: 10.1021/ol302098u.

    Article  Google Scholar 

  • Lázár, L., Csávás, M., Hadházi, Á., Herczeg, M., Tóth, M., Somsák, L., Barna, T., Herczegh, P., & Borbás, A. (2013) Systematic study on free radical hydrothiolation of unsaturated monosaccharide derivatives with exo- and endocyclic double bonds. Organic & Biomolecular Chemistry, 11, 5339–5350.DOI: 10.1039/c3ob40547h.

    Article  Google Scholar 

  • Liu, L., McKee, M., & Postema, M. H. D. (2001) Synthesis of C-saccharides and higher congeners. Current Organic Chemistry, 5, 1133–1167.DOI: 10.2174/1385272013374699.

    Article  CAS  Google Scholar 

  • Lopez, M., Bornaghi, L. F., Driguez, H., & Poulsen, S. A. (2011) Synthesis of sulfonamide-bridged glycomimetics. The Journal of Organic Chemistry, 76, 2965–2975.DOI: 10.1021/jo2001269.

    Article  CAS  Google Scholar 

  • Matta, K. L., Girotra, R. N., & Barlow, J. J. (1975) Synthesis of p-nitrobenzyl and p-nitrophenyl 1-thioglycopyranosides. Carbohydrate Research, 43, 101–109.DOI: 10.1016/s0008-6215(00)83976-2.

    Article  CAS  Google Scholar 

  • Mugunthan, G., Sriram, D., Yogeeswari, P., & Kartha, K. P. R. (2011) Synthetic analogues of mycobacterial arabinogalactan linkage-disaccharide part II: Synthesis and preliminary screening of lipophilic O-alkyl glycosides. Carbohydrate Research, 346, 2401–2405.DOI: 10.1016/j.carres.2011.08.027.

    Article  CAS  Google Scholar 

  • Praly, J. P. (2000) Structure of anomeric glycosyl radicals and their transformations under reductive conditions. Advances in Carbohydrate Chemistry and Biochemistry, 56, 65–151.DOI: 10.1016/s0065-2318(01)56003-5.

    Article  CAS  Google Scholar 

  • Prosperi, D., Ronchi, S., Lay, L., Rencurosi, A., & Russo, G. (2004) Efficient synthesis of unsymmetrical ureidolinked disaccharides. European Journal of Organic Chemistry, 2004, 395–405.DOI: 10.1002/ejoc.200300483.

    Article  Google Scholar 

  • Robina, I., Vogel, P., & Witczak, Z. (2001) Synthesis and biological properties of monothiosaccharides. Current Organic Chemistry, 5, 1177–1214.DOI: 10.2174/1385272013374743.

    Article  CAS  Google Scholar 

  • Staderini, S., Chambery, A., Marra, A., & Dondoni, A. (2012) Free-radical hydrothiolation of glycals: A thiol-ene-based synthesis of S-disaccharides. Tetrahedron Letters, 53, 702–704.DOI: 10.1016/j.tetlet.2011.11.140.

    Article  CAS  Google Scholar 

  • Stellenboom, N., Hunter, R., & Caira, M. R. (2010) One-pot synthesis of unsymmetrical disulfides using 1-chlorobenzotriazole as oxidant: Interception of the sulfenyl chloride intermediate. Tetrahedron, 66, 3228–3241.DOI: 10.1016/j.tet.2010.02.077.

    Article  CAS  Google Scholar 

  • Szilágyi, L., Illyés, T. Z., & Herczegh, P. (2001) Elaboration of a novel type of interglycosidic linkage: Syntheses of disulfide disaccharides. Tetraheedron Letters, 42, 3901–3903.DOI: 10.1016/s0040-4039(01)00578-0.

    Article  Google Scholar 

  • Szilágyi, L., & Varela, O. (2006) Non-conventional glycosidic linkages: Syntheses and structures of thiooligosaccharides and carbohydrates with three-bond glycosidic connections. Current Organic Chemistry, 10, 1745–1770.DOI: 10.2174/138527206778249874.

    Article  Google Scholar 

  • Tóth, M., & Somsák, L. (2001) exo-Glycals from glycosyl cyanides. First generation of C-glycosylmethylene carbenes from 2,5- and 2,6-anhydroaldose tosylhydrazones. Journal of the Chemical Society, Perkin Transactions 1, 942–943.DOI: 10.1039/b102963k.

    Article  Google Scholar 

  • Tóth, M., Kóvér, K. E., Bényei, A., & Somsák, L. (2003) C-Glycosylmethylene carbenes: Synthesis of anhydro-aldose to-sylhydrazones as precursors; generation and a new synthetic route to exo-glycals. Organic & Biomolecular Chemistry, 1, 4039–4046.DOI: 10.1039/b307378e.

    Article  Google Scholar 

  • Tóth, M., Kun, S., Somsák, L., & Goyard, D. (2011) Preparation of exo-glycals from 2,6-anhydro-aldose-tosylhydrazones. In P. Kovac (Ed.) Carbohydrate chemistry: Proven synthetic methods (pp. 365–373). Boca Raton, FL, USA: CRC Press.

    Google Scholar 

  • Witczak, Z. J., & Culhane, J. M. (2005) Thiosugars: New perspectives regarding availability and potential biochemical and medicinal applications. Applied Microbiology and Biotechnology, 69, 237–244.DOI: 10.1007/s00253-005-0156-x.

    Article  CAS  Google Scholar 

  • Witczak, Z. J., Lorchak, D., & Nguyen, N. (2007) A click chemistry approach to glycomimetics: Michael addition of 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranose to 4-deoxy-1,2-O-isopropylidene-L-glycero-pent-4-enopyranos-3-ulose — a convenient route to novel 4-deoxy-(1→5)-5-C-thiodisaccharides. Carbohydrate Research, 342, 1929–1931.DOI: 10.1016/j.carres.2007.06.005.

    Article  CAS  Google Scholar 

  • Witczak, Z. J., & Bielski, R. (2013) Click chemistry in glycoscience: New developments and strategies. New York, NY, USA: Wiley.

    Book  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Applied Chemistry, University of Debrecen, Egyetem tér 1, H-4032, Debrecen, Hungary

    László Lázár

  2. Department of Pharmaceutical Chemistry, University of Debrecen, PO Box 70, H-4010, Debrecen, Hungary

    Magdolna Csávás & Anikó Borbás

  3. Department of Organic Chemistry, University of Debrecen, PO Box 20, H-4010, Debrecen, Hungary

    Marietta Tóth & László Somsák

Authors
  1. László Lázár
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Magdolna Csávás
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Marietta Tóth
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. László Somsák
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Anikó Borbás
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Anikó Borbás.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lázár, L., Csávás, M., Tóth, M. et al. Thio-click approach to the synthesis of stable glycomimetics. Chem. Pap. 69, 889–895 (2015). https://doi.org/10.1515/chempap-2015-0085

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1515/chempap-2015-0085

Keywords

Search

Navigation