P. Allevi et al. / Bioorg. Med. Chem. Lett. 14 (2004) 3319–3321
3321
12. Leigh, S. D.; Julia Ju, H.-S.; Lundgard, R.; Daniloff, G.
Y.; Liu, V. J. Immunol. Methods 1998, 220, 169–178.
13. Casetta, B.; Romanello, M.; Moro, L. Rapid Commun.
Mass Spectrosc. 2000, 14, 2238–2241, and references cited
therein.
14. Tenni, R.; Rimoldi, D.; Zanaboni, G.; Cetta, G.; Castel-
lani, A. A. Ital. J. Biochem. 1984, 33, 117–127.
15. Selected data for (2S,5R)-2,6-diamino-5-[a-D-glucopyr-
afford the target glycoconjugate 1 as ditrifluoroacetate
salt.
Our work makes available in a relatively easy way the
commercially unavailable hydroxylysine glycoconjugate
1, and facilitates its use in biological researches on col-
lagen. More generally, we feel that present results
appear to be very attractive for the assembling, via our
previously reported protocols,17;18 of other more com-
plex glycoside of cross-linked hydroxylysine (glycosyl-
ated pyridinolines) present in collagen.25
anosyl-(1 fi 2)-b-
D-galactopyranosyloxy]hexanoic acid 1
difluoroacetate (C18H36N2O13 2CF3COOÀ): a syrup; ½a
D
+21.9( c 1, MeOH); 1H NMR (D2O): 5.34 (1H, d, J ¼ 3:6,
100-H), 4.62 (1H, d, J ¼ 7:5, 10-H), 4.11 (1H, m, 5-H), 4.08
(1H, dd, J ¼ 6:5, 6.5, 2-H), 3.66 (1H, dd, J ¼ 9:5, 7.5,
20-H), 3.50 (1H, dd, J ¼ 9:9, 3.6, 200-H); 13C NMR (D2O):
172.4 (C-1), 173.7 (q, JCF ¼ 34:3, CF3COOÀ), 117.3 (q,
JCF ¼ 289:9, CF3COOÀ), 102.5 (C-10), 98.5 (C-100), 72.5
(C-5), 53.4 (C-2), 43.6 (C-6). This and all other new
compounds gave correct C, H, and N elemental analyses
that were within 0.3% of the theoretical values.
Acknowledgements
This work was supported financially by Italian MIUR
ꢀ
(Ministero dell’Istruzione, dell’Universita e della Ric-
erca).
16. Schmidt, R. R. Angew. Chem., Int. Ed. Engl. 1986, 25,
212–235.
17. (a) Allevi, P.; Galligani, M.; Anastasia, M. Tetrahedron:
Asymmetry 2002, 13, 1901–1910; (b) Allevi, P.; Anastasia,
M. Tetrahedron: Asymmetry 2000, 11, 3151–3160;
(c) Allevi, P.; Anastasia, M. Tetrahedron: Asymmetry
2003, 14, 2005–2012.
18. For our previous work on pyridinoline synthesis, see also:
Anastasia, L.; Anastasia, M.; Allevi, P. J. Chem. Soc.,
Perkin Trans. 1 2001, 2404–2408; Allevi, P.; Longo, A.;
Anastasia, M. J. Chem. Soc., Perkin Trans. 1 1999, 2867–
2868; Allevi, P.; Longo, A.; Anastasia, M. J. Chem. Soc.,
Chem. Commun. 1999, 559–560.
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pyranosyloxy)hexanoate tert-butyl ester 4: an oil; ½aD +7.9
1
(c 1, CHCl3); H NMR (CDCl3): 5.34 (1H, dd, J ¼ 10:0,
0
7.9, 20-H), 4.43 (1H, d, J ¼ 7:9 , 1-H), 4.01 and 3.92
(2 · 1H, 2 · d, J ¼ 14:7, ClCHHCO2), 3.63 (1H, m, 5-H),
1.44 (9H, s, C(CH3)3); 13C NMR (CDCl3): 171.0 (C-1),
165.9(ClCH 2CO2), 155.8 (NHCO), 101.5 (C-10), 54.4
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D
2)-(3,4,6-tri-O-benzyl-b-D-galactopyranosyloxy)]hexanoate
tert-butyl ester 6: an oil; ½a +25.6 (c 1, CHCl3); 1H NMR
D
(CDCl3): 5.62 (1H, d, J ¼ 3:5, 100-H), 4.63 (1H, d, J ¼ 7:7,
10-H), 4.21 (1H, dd, J ¼ 10:0, 7.7, 20-H), 3.88 (1H, m, 5-H),
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