10.1002/chem.201705511
Chemistry - A European Journal
water in 60 min delivered product H in 98% yield (1.758 µmol,
1.800 mg) over two steps as white solid. 1H-NMR (400 MHz,
D2O): δ = 5.39 (d, J = 1.8 Hz, 1H, GlcN-1), 5.04 (d, J = 3.5 Hz,
1H, Gal-1), 4.92 (d, J = 1.4 Hz, 1H, Gal’-1), 4.39 (d, J = 7.6 Hz,
1H, Man-1), 4.05 – 3.33 (m, 38H), 1.55 – 1.47 (m, 4H, -CH2-),
1.18 – 1.12 (m, 4H, -CH2-) ppm; 13C-NMR from HSQC: (101
MHz, D2O, coupled): δ = 101.1, 100.8, 99.9, 98.2, 80.0. 77.7,
75.2, 75.1, 73.6, 73.4, 72.8, 71.3, 70.7, 70.1, 69.6, 69.5, 69.1,
69.0,68.7, 67.3, 66.9, 65.4,62.9, 61.5, 60.9, 60.8, 22.1, 17.33,
Keywords: carbohydrates • glycolipid • GPI synthesis •
glycosylphosphatidylinositol • Trypanosoma brucei
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9.9, ESI-MS: m/z Mcalcd for C33H59NO25 = 869.3376; Mfound
=
887.3883 [M+NH4]+
D-mannopyranosyl-α-(1 → 2)-D-mannopyranosyl-α-(1 → 6)-3-O-
(D-galactopyranosyl-α-(1 6)-D-galactopyranosyl-α-)-D-
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→
mannopyranosyl-α-(1 → 4)-2-amino-2-deoxy-D-glucopyranosyl-
α-(1-6)-myo-inositol (I): Alcohol 69 (2.372 µmol, 8.0 mg) was
dissolved in a 5:2 mixture of ACN and DCM. Scandium triflate
(4.744 µmol, 2.3 mg) and 100 µl water were added and the
mixture was refluxed for three hours. The solvent was removed
in vacuo, the residue dissolved in DCM, washed with saturated
NaHCO3-solution, dried with MgSO4 and concentrated under
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chromatography using an eluent of hexane and ethyl acetate
and diretly used for the next step. Rf = 0.4 (2:1; Hex/EtoAc).
Approximately 10 mL of ammonia were condensed in a flask
and methanol (2 drops) was added. Sodium was added in small
pieces until a dark blue color established. The diol was dissolved
in THF and added to the ammonium solution at -78°C. At this
temperature the reaction was stirred for 1 h. The reaction was
quenched by adding methanol and ammonia was blown off
using a stream of nitrogen. The pH of the resulting solution was
adjusted with glacial acetic acid to 7-8. The reaction was
concentrated under reduced pressure and the residue was
purified on a Sephadex G 15 column using 5% ethanol in water
as eluent. After lyophilization, product I was obtained in 44%
yield (1.042 µmol, 1.200 mg) as white solid over two steps.
1H-NMR (400 MHz, D2O): δ = 5.26 (s, 1H, GlcN-1), 5.10 (d,
J = 3.7 Hz, 1H, Gal-1), 5.06 (d, J = 4.0 Hz, 1H, Gal‘-1), 5.04 (d,
J = 1.6 Hz, 1H, Man-1), 4.92 (d, J = 1.8 Hz, 1H, Man‘-1), 4.86 (d,
J = 3.6 Hz, 1H, Man‘‘-1), 4.29 – 4.25 (m, 1H), 4.22 (d, J = 2.8 Hz,
1H), 4.01 – 3.44 (m, 37H), 3.41 (dd, J = 10.0 Hz, 2.9 Hz, 1H),
3.26 (t, J = 9.1 Hz, 1H), 2.68 (dd, J = 10.2 Hz, 3.7 Hz, 1H) ppm;
13C-NMR (151 MHz, D2O): δ = 102.2 (Man’-1), 101.5 (Gal‘-1),
101.0 (GlcN-1), 99.8 (Gal-1), 98.7 (Man‘‘-1), 98.1 (Man-1), 80.8,
80.7, 78.6, 78.4, 78.4, 76.3, 74.2, 73.7, 73.1, 72.9, 72.6, 72.4,
72.4, 71.4, 70.9, 70.9, 70.7, 70.2, 70.2, 69.9, 69.7, 69.7, 69.5,
69.3, 69.2, 69.1, 68.7, 68.1, 66.8, 66.7, 61.0 ppm; ESI-MS: m/z
Mcalcd for C42H73NO35 = 1151.3963; Mfound = 1152.4642 [M]+.
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Acknowledgements
This research was supported by the Max Planck Society and the
RIKEN-Max Planck Joint Research Center for Systems
Chemical Biology. Dr. Maurice Grube is thankful for a doctoral
scholarship provided by the Beilstein-Institut zur Förderung der
chemischen Wissenschaften and a scholarship from the federal
state of lower Saxony. Dr. Monika Garg received a doctoral
scholarship from the International Max Planck Research School
on Multiscale Biosystems of the MPIKG. We thank Olaf
Niemeyer for NMR Service and Dr. Yu-Hsuan Tsai and Dr.
Sebastian Götze for valuable building block precursors. We
thank Dr. Martin Scobie for carefully proofreading the manuscript.
[29] Z. Li, L. Zhu, J. Kalikanda, Tetrahedron Lett. 2011, 52, 5629-5632.
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