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Construction of Disaccharide N-Glycopeptides—Synthesis of the Linkage Region of the Transmembrance-Neuraminidase of an Influenza Virus^†^‡

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Prof. Dr. Horst Kunz

Institut für Organische Chemie der Universität, Johann-Joachim-Becher-Weg 18–20, D-6500 Mainz (FRG)

Institut für Organische Chemie der Universität, Johann-Joachim-Becher-Weg 18–20, D-6500 Mainz (FRG)Search for more papers by this author

Dr. Herbert Waldmann,

Dr. Herbert Waldmann

Institut für Organische Chemie der Universität, Johann-Joachim-Becher-Weg 18–20, D-6500 Mainz (FRG)

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Prof. Dr. Horst Kunz,

Corresponding Author

Prof. Dr. Horst Kunz

Institut für Organische Chemie der Universität, Johann-Joachim-Becher-Weg 18–20, D-6500 Mainz (FRG)

Institut für Organische Chemie der Universität, Johann-Joachim-Becher-Weg 18–20, D-6500 Mainz (FRG)Search for more papers by this author

Dr. Herbert Waldmann,

Dr. Herbert Waldmann

Institut für Organische Chemie der Universität, Johann-Joachim-Becher-Weg 18–20, D-6500 Mainz (FRG)

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First published: October 1985

https://doi.org/10.1002/anie.198508831

Citations: 51

^†

This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.

^‡

Dedicated to Professor Günter Viktor Schulz on the occasion of his 80th birthday

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The glycopeptide fragments 1 and 2 from immunologically interesting N-glyco-proteins can be obtained in a highly selective manner from a cleavable allylester. 1 and 2 are model compounds for the study of recognition mechanisms at cell membrances.

References

1 Summary: E. F. Neufeld, G. Ashwell in W. J. Lennarz (Ed.): The Biochemistry of Glycoproteins and Proteoglycans, Plenum Press, New York 1980.
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2 C. W. Ward, T. C. Ellman, A. A. Azad, Biochem. J. 207 (1982) 91.
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5 H. Kunz, H. Waldmann, Angew. Chem. 96 (1984) 49;
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Angew. Chem. Int. Ed. Engl. 23 (1984) 71; here the reaction takes place within 4 h at room temperature in tetrahydrofuran (THF)/dimethyl sulfoxide (DMSO) (4:1).
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6 Preparation according to: H. Waldmann, H. Kunz, Liebigs Ann. Chem. 1983, 1712.
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7 Procedure: A solution of 11a (0.28g, 0.26 mmol) in anhydrous dioxane (10 mL) was treated under argon and in the absence of light with 30 mg (0.026 mmol) of tetrakis (triphenylphosphane) palladium (0) and then dropwise with 0.26 g (3 mmol) of morpholine. The mixture was stirred for 12 h at room temperature, evaporated to dryness, and the resulting C-Terminally deblocked di-N-acetylchitobiosaminyl tripeptide 12 purified chromatographically on silica gel, the impurities being first removed with chloroform/ethanol (9:1) and 12 then being eluted with methanol. Yield 0.19 g (71%); m.p. 218–220°C; [α]22/D = 6.2 (c = 0.2, DMSO). (−270-MHz 1H NMR [D6] DMSO): δ = 8.51 (d, J = 10 Hz, 1H, γ-NH Asn), 8.05 (d, J = 10 Hz, 1H, NH), 7.94 (d, J = 8.5 Hz, 1H, NH), 7.87 (d, J = 9 Hz, 1H, NH), 7.53 (d, J = 7.5 Hz, 1H, NH), 6.86 (d, J = 9.2 Hz, 1H, NH urethane), 5.11 (dd, J(H1/NH) = 10, J(H1/H2) = 9.5 Hz, 1H, H1), 4.68 (d, J(H1′/ H2′) = 8.3 Hz, 1H, H1′), 2.49 (dd, Jgem = 11.9, Jvic = 7.5 Hz, 1H, β-CHa Asn), 2.03, 2.0, 1.94, 1.93 and 1.91 (5s, 15H, 5CH₃COO), 1.74 (s, 6H, 2CH₃CONH), 1.38 (s, 9H, (CH₃)₃C), 1.20 (d, J = 6 Hz, 3H, CH(OH)CH₃), 0.95 (d, J = 6.2 Hz, 3H, CH-CH₃).
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8 M. p. 202°C; [α]22/D −3.3 (c = 0.1, DMSO).—FAB mass spectrum : m/z_calc 1219, m/z _obs 1258 ((M+K) +). -270- MHz 1H NMR ([D6]- DMSO): δ = 8.5–8.4 (m, 2H, NH), 8.22 (d, J = 7.6 Hz, 1H, NH), 8.02 (d, J = 9.1 Hz, 1H, NH), 7.83 (d, J = 7.5 Hz, 1H, NH), 7.24 (d, J = 7.8 Hz, 1H, NH), 5.9 (ddt, 1H, CH = CH₂), 5.31 (dd, J_trans = 17.3, J_gem = 1.7 Hz, 1H, CH = CH_2trans), 5.19 (dd, J_cis = 9.6, J_gem = 1.7 Hz, 1H, CH = CH₂), 4.68 (d, J(H1′/H2′) = 8.2 Hz, 1H, H1′), 4.57 (d, J = 4.8 Hz, 2H, CH₂-CH = CH₂), 2.04, 2.01, 1.95, 1.94 and 1.90 (5s, 15H, 5CH₃-COO), 1.74 (s, 6H, 2CH₃CONH), 1.35 (s, 9H, (CH₃)₃C).
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9 Procedure: A solution of fully protected chitobiosly tripeptide ester 11b (0.45 g, 0.39 mol) in a cold saturated solution of ammonia in methanol (20 mL) was stirred for 2 d at room temperature. The reaction mixture was then evaporated to dryness and the residual product (15) purified by two recrystallizations from methanol/chloroform. Yield 0.3 g (86%), m. p. 267°C; [α]22/D = −14.4 (c = 0.1, H₂O). -FAB mass spectrum: m/z_calc = 885.8, m/z_obs = 887 (M+1), 909 (M+Na)+. -470-MHz 1H NMR (D₂O): δ = 7.38 (d, J = 7.3 Hz, 2H, 2o-H C₆H₅), 7.33 (t, J = 6.7 Hz, 1H, p-H C₆H₅), 7.29 (t, J = 6.2 Hz, 2H, 2m-H C₆H₅), 5.05 (d, J(H1/H2) = 9.5 Hz, 1H, H1), 4.59 (d, J(H1′/H2′) = 8.4 Hz, 1H, H1′), 3.13 (dd, J_vic = 7.9, J_vic = 8.4 Hz, 2H, β-CH₂ Phe), 2.72 (dd, J_vic = 16, J_gem = 5.6 Hz, 1H, β-CHa Asn), 2.6–2.55 (m, 1H, β-CHb Asn), 2.06 and 2.02 (2s, 6H, 2CH₃-CONH), 1.41 (s, 9H, (CH₃)₃C), 1.16 (d, J = 6.2 Hz, 3H, CH(OH)-CH₃).
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Volume24, Issue10

October 1985

Pages 883-885

Construction of Disaccharide N-Glycopeptides—Synthesis of the Linkage Region of the Transmembrance-Neuraminidase of an Influenza Virus^†^‡

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Construction of Disaccharide N-Glycopeptides—Synthesis of the Linkage Region of the Transmembrance-Neuraminidase of an Influenza Virus†‡

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Construction of Disaccharide N-Glycopeptides—Synthesis of the Linkage Region of the Transmembrance-Neuraminidase of an Influenza Virus^†^‡