1868
O. Schwardt et al. / Bioorg. Med. Chem. 9 (2001) 1857–1869
to H-6,60) d 4.51, 3.80, 3.75, 3.72, 3.54, 3.83 and 4.01;
b-gal-unit (H-1 to H-6,60) d 4.55, 3.69, 3.79, 4.20, 3.74,
3.77 and 3.78; a-gal-unit (H-1 to H-6,60) d 5.17, 3.88,
3.98, 4.04, 4.22, 3.70 and 3.72; glcA-unit [H-1 to H-5,
H-10, C(CH3)3] d 3.40, 3.29, 3.51, 3.51, 3.84, 3.24 and
3.44, 1.43; aglycon (H-1 to H-3, OCH2Ph, C6H5) d 3.59
and 3.95, 1.73, 3.16 and 3.22, 5.13, 7.39–7.51. 13C NMR
(D2O) glcN-unit (C-1 to C-6) d 101.2, 55.5, 72.8, 79.4,
74.9, 60.4; b-gal-unit (C-1 to C-6) d 103.6, 70.1, 77.7,
65.2, 75.3, 61.3; a-gal-unit (C-1 to C-6) d 95.9, 68.3,
69.7, 69.5, 71.6, 61.4; glcA-unit [C-1 to C-5, C-10,
C(CH3)3] d 78.6, 71.1, 77.0, 72.1, 78.9, 41.1, 27.7; aglycon
(C-1 to C-3, OCH2Ph, C6H5) d 67.6, 28.9, 37.2, 67.1,
127.0-129.8. [a]D +39 (c 0.53, H2O). HRMS calcd for
C41H65N3O24ꢀH 982.3880: found MSꢀH 982.3881.
67.0, 127.4–130.1. [a]D +31 (c 0.50, H2O). HRMS calcd
for C41H65N3O24+Na 1006.3856: found MS+Na
1006.3868.
Acknowledgements
The authors thank Dr. M. Streiff and his team for
cloning and overexpression of the a(1-3)gal transferase.
References and Notes
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16. Galili, U.; Anaraki, F. Glycobiology 1995, 5, 775.
17. Baisch, G.; Ohrlein, R. Angew. Chem. Int. Ed. Engl. 1996,
35, 1812.
18. McKane, W.; Lee, J.; Preston, R.; Hacking, A.; Simpson,
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tation 1998, 66, 626.
8-Methoxycarbonyloctyl ꢁ-D-galactopyranosyl-(1!3)-
ꢀ-D-galactopyranosyl-(1!4)-2-deoxy-2-(1-deoxy-1-tert-
butoxycarbonylaminomethyl-ꢀ-D -galactohexopyranosy-
luronamide)-ꢀ-D-glucopyranoside 8k. According to GP
C, 10.0 mg (12.5 mmol) of sugar 6k were dissolved in 450
mL cacodylate-buffer and incubated with 20.1 mg (32.9
mmol) UDP-gal, 0.6 mg BSA, 10.4 mg (52.6 mmol)
MnCl2ꢂ4H2O, 2 mL CIAP, and 150 mL a(1-3)gal-t (300
mU) for 1 day to give 9.3 mg (77%) of the title sugar.
1H NMR (D2O, 400.1 MHz) glcN-unit (H-1 to H-6,60) d
4.78, 3.68, 3.98, 3.75, 3.64, 3.87 and 4.03; b-gal-unit (H-1
to H-6,60) d 4.56, 3.69, 3.81, 4.20, 3.76, 3.81 and 3.84;
a-gal-unit (H-1 to H-6,60) d 5.17, 3.90, 3.98, 4.04, 4.22,
3.75 and 3.76; galA-unit [H-1 to H-5, H-10, C(CH3)3] d
3.39, 3.58, 3.73, 4.29, 4.14, 3.31 and 3.65, 1.46; aglycon
(H-2 to H-9, OCH3) d 2.40, 1.62, 1.31, 1.32, 1.57, 3.66
and 3.89, 3.70. 13C NMR (D2O) glcN-unit (C-1 to C-6) d
100.2, 56.4, 72.5, 79.6, 74.9, 60.5; b-gal-unit (C-1 to C-6)
d 103.6, 70.1, 77.4, 65.2, 75.3, 61.3; a-gal-unit (C-1 to C-6)
d 95.9, 68.3, 69.7, 69.5, 71.5, 61.3; glcA-unit [C-1 to C-5,
C-10, C(CH3)3] d 79.4, 68.2, 73.9, 69.9, 78.5, 41.5, 27.9;
aglycon (C-2 to C-9, OCH3) d 34.3, 25.0, 28.6, 25.4, 28.3,
71.3, 52.3. [a]D +36 (c 0.52, H2O). HRMS calcd for
C40H70N2O24+Na 985.4216: found MS+Na 985.4213.
3-Benzoxycarbonylaminopropyl
ꢁ-D-galactopyranosyl-
19. Simanek, E. E.; McGarvey, G. J.; Jablonowski, J. A.;
Wong, C.-H. Chem. Rev. 1998, 98, 833.
(1!3)-ꢀ-D-galactopyranosyl-(1!4)-2-deoxy-2-(1-deoxy-
1-tert-butoxycarbonylaminomethyl-ꢀ-D-galactohexopyra-
nosyluronamide)-ꢀ-D-glucopyranoside 9k. According to
GP C, 9.0 mg (11.0 mmol) of sugar 7k were dissolved in
400 mL cacodylate-buffer and incubated with 17.7 mg
(29.0 mmol) UDP-gal, 0.5 mg BSA, 9.2 mg (46.5 mmol)
MnCl2ꢂ4H2O, 2 mL CIAP, and 200 mL a(1-3)gal-t (400
mU) for 1 day to give 10.0 mg (92%) of the title sugar.
1H NMR (D2O, 400.1 MHz) glcN-unit (H-1 to H-6,60) d
4.59, 3.74, 3.82, 3.70, 3.54, 3.80 and 3.99; b-gal-unit (H-1
to H-6,60) d 4.58, 3.69, 3.81, 4.21, 3.72, 3.75 (2 H); a-gal-
unit (H-1 to H-6,60) d 5.17, 3.86, 3.99, 4.05, 4.22, 3.75
(2 H); galA-unit [H-1 to H-5, H-10, C(CH3)3] d 3.40, 3.56,
3.69, 4.27, 4.18, 3.29 and 3.53, 1.45; aglycon (H-1 to H-3,
OCH2Ph, C6H5) d 3.62 and 3.86, 1.75, 3.18 and 3.27,
5.13, 7.35–7.48. 13C NMR (D2O) glcN-unit (C-1 to C-6)
d 100.9, 55.9, 73.0, 79.6, 75.0, 60.4; b-gal-unit (C-1 to C-6)
d 103.5, 70.1, 77.8, 65.3, 75.2, 61.2; a-gal-unit (C-1 to
C-6) d 96.1, 68.3, 69.6, 69.6, 71.7, 61.2; galA-unit [C-1 to
C-5, C-10, C(CH3)3] d 79.1, 67.9, 73.9, 69.8, 78.4, 41.3, 27.9;
aglycon (C-1 to C-3, OCH2Ph, C6H5) d 67.8, 28.9, 37.4,
20. Mammen, M.; Choi, S.-K.; Whitesides, G. M. Angew.
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