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Synlett 2013; 24(6): 719-722
DOI: 10.1055/s-0032-1318480
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of S-Linked N-Acetylneuraminic Acid Derivatives via Photoinduced Thiol–ene and Thiol–yne Couplings

Magdolna Csávás*
a   Department of Pharmaceutical Chemistry, Medical and Health Science Center, University of Debrecen, PO Box 70, 4010 Debrecen, Hungary   Fax: +36(52)512914   eMail: csavas.magdolna@science.unideb.hu   eMail: borbas.aniko@pharm.unideb.hu
b   Research Group for Carbohydrates of the Hungarian Academy of Sciences, P.O. Box 94, 4010 Debrecen, Hungary
,
Mihály Herczeg
b   Research Group for Carbohydrates of the Hungarian Academy of Sciences, P.O. Box 94, 4010 Debrecen, Hungary
c   Department of Organic Chemistry, University of Debrecen, PO Box 20, 4010 Debrecen, Hungary
,
Anikó Borbás*
a   Department of Pharmaceutical Chemistry, Medical and Health Science Center, University of Debrecen, PO Box 70, 4010 Debrecen, Hungary   Fax: +36(52)512914   eMail: csavas.magdolna@science.unideb.hu   eMail: borbas.aniko@pharm.unideb.hu
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Publikationsverlauf

Received: 23. Januar 2013

Accepted after revision: 26. Februar 2013

Publikationsdatum:
08. März 2013 (online)

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Abstract

Thio-linked mono- and bivalent mimetics of α(2→3) and α(2→6)-linked sialosides were prepared by photoinduced hydrothiolation of alkenes and alkynes with the 2-mercapto sialic acid. Thiosialylation of 6-O-allyl- or 3-O-allyl-substituted galactose derivatives has been carried out by the thiol–ene click reaction. Double thiosialylation has also been achieved via thiol–yne chemistry using propargylated galactose derivatives as the alkyne components and the peracetylated 2-mercapto sialic acid as the thiol.

Key words

carbohydrates - N-acetylneuraminic acid - radical additions - thiol–ene/thiol–yne coupling - thiosialosides

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
  • Supporting Information
 

  • References and Notes

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  • 21 NMR Data for Compound 12 1H NMR (360 MHz, CDCl3): δ = 8.06–7.26 (m, 10 H, arom.), 5.60–5.43 (m, 3 H), 5.30–5.27 (m, 2 H), 5.14–5.12 (m, 1 H), 4.85–4.75 (m, 2 H), 4.57 (d, 1 H, J = 7.9 Hz), 4.50 (t, 1 H, J = 10.0 Hz), 4.45–4.35 (m, 3 H), 4.29–4.24 (m, 1 H), 4.15–3.87 (m, 8 H), 3.80–3.49 (m, 16 H), 2.60–2.54 (m, 2 H), 2.14–1.25 (m, 23 H) ppm. 13C NMR (90 MHz, CDCl3): δ = 170.9, 170.6, 170.1, 170.0 (6 C, CO), 133.5-126.4 (10 C, arom), 102.3, (2 C, Cac), 101.1 (C-1), 83.3 (C-2′), 78.5, 73.9, 73.2, 69.6, 68.3, 67.1, 66.7, 66.4 (8 C, skeleton carbons), 70.5, 69.3, 69.1, 68.0, 66.8 (5 C, 4 × CH2, C-6), 63.0 (C-9′), 52.8 (C-5′), 35.1, 32.7, 29.3, 29.2, 29.1, 25.8, 25.7, 25.5, 23.8, 23.7 (10 C, CH2), 23.1 (CH3,NHAc), 21.2, 20.8 (4 C, CH3,Ac) ppm.
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  • 23 NMR Data for Compound 15 1H NMR (500 MHz, CDCl3): δ = 6.46 (d, 0.17 H, J = 9.5 Hz, SCH=CHCH2), 6.35 (d, 0.83 H, J = 15.5 Hz, SCH=CHCH2), 5.72–5.69 (m, 1 H, SCH=CHCH2), 5.48–5.31 (m, 3 H), 5.04–5.01 (m, 1 H), 4.90–4.85 (m, 2 H), 4.51–4.49 (m, 2 H), 4.40–4.17 (m, 3 H), 4.15–4.05 (m, 3 H), 4.01–3.75 (m, 10 H), 3.60–3.42 (m, 3 H), 2.75–2.72 (m, 2 H), 2.22–1.84 (m, 24 H), 1.59–1.28 (m, 14 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 170.7, 170.5, 170.4, 170.3, 170.2, 170.1, 170.0, 169.8, 169.4, 169.3, 168.1, 167.7 (CO), 130.5, 128.4, 122.2, 121.9 (CH), 102.3 (Cac), 101.2 (C-1), 77.2, 77.0, 76.7, 76.6, 76.1, 74.9, 74.4, 74.1, 70.7, 70.4, 69.8, 69.2, 68.8, 68.0, 67.3, 67.0, 66.7, 66.5, 65.9 (skeleton carbons), 69.5, 69.4, 67.5 (CH2), 62.2, 62.1, 61.9 (C-6), 53.0 (OCH3), 49.2, 49.0 (C-5), 37.5, 37.3, 35.1, 29.3, 29.1, 25.74 (CH2), 25.6, 23.7, 23.0, 21.1, 21.0, 20.9, 20.7, 20.6 (CH3) ppm