N. Ruiz et al. / Carbohydrate Research 346 (2011) 1581–1591
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3.34 (m, 2H, H-5A, H-5B), 3.27 (m, 2H, C-1A-O-CHa2, H-3C), 3.09 (m,
1H, H-5C), 2.93–2.86 (m, 2H, CH2N3), 2.15, 2.14, 2.13, 2.04, 2.03,
2.00, 1.96, 1.90, 1.82 (s, 3H, OCH3), 1.41–1.27 (m, 4H, 2 ꢃ CH2),
1.13–1.07 (m, 2H, CH2). 13C NMR (126 MHz, CDCl3): 170.9, 170.5,
170.3, 170.2, 170.1, 170.0, 169.4, 169.2, 168.5, 138.6, 138.4,
138.3, 138.2, 138.1, 138.0, 137.9, 137.5, 134.1, 133.6, 131.7,
131.6, 131.4, 131.3, 128.9, 128.4, 128.3, 128.2, 128.1, 128.0,
127.9, 127.8, 127.6, 127.5, 127.4, 127.3, 127.2, 127.1, 126.9,
126.2, 123.7, 123.4, 123.1, 101.0 (C-1C, JC-1-H-1 = 158.4 Hz), 100.5
(C-1F, JC-1-H-1 = 170.2 Hz), 99.8 (C-1G, JC-1-H-1 = 173.1 Hz), 98.3 (C-
1D, JC-1-H-1 = 170.2 Hz), 98.1 (C-1B, JC-1-H-1 = 161.4 Hz), 97.3 (C-1E, J
C-1-H-1 = 164.3 Hz), 97.2 (C-1A, JC-1-H-1 = 167.2 Hz), 78.2, 77.9, 76.1,
75.1, 75.0, 74.9, 74.8 74.6, 74.5, 74.1, 73.4, 73.2, 72.7, 72.6, 72.0,
71.6, 71.5, 70.9, 69.6, 69.5, 68.9, 68.7, 68.6, 68.5, 68.2, 68.1, 65.6,
65.4, 62.6, 62.4, 61.5, 56.7, 56.5, 55.7, 54.5, 51.1, 28.7, 28.3, 23.0,
21.1, 21.0, 20.8, 20.7, 20.6, 20.5. HRMS calcd for C152H162N6O48Na
[M+Na]+ 2862.0317, found 2862.0366.
2H, Ar), 6.83–6.78 (m, 8H, Ar), 5.75 (dd, J = 9.0, 10.8 Hz, 1H, H-
3E), 5.65 (d, J = 8.8 Hz, 1H, H-1E), 5.52 (dd, J = 1.6, 2.6 Hz, 1H, H-
2D), 5.46 (dd, J = 2.7, 9.5 Hz, 1H, H-3G), 5.32–5.26 (m, 3H, H-4E,
H-2G, H-1A), 5.18 (t, J = 9.9 Hz, 1H, H-4F), 5.11 (d, J = 12.6 Hz, 1H,
CHBn), 4.98–4.90 (m, 5H, H-3F, H-1D, H-1G, H-1B, CHBn), 4.82 (m,
2H, 2 ꢃ CHBn), 4.72 (m, 2H, 2 ꢃ CHBn), 4.65–4.33 (m, 16H, H-2E,
H-6aE, H-1F, H-1C, 12 ꢃ CHBn), 4.28–4.12 (m, 8H, H-2A, H-2B, H-
6bE, H-2F, H-3A, H-4A, H-3B, H-4B), 4.04–3.81 (m, 7H, H-6aG, H-5E,
H-5G, H-4D, H-4C, H-4G, H-3D), 3.75–3.20 (m, 18H, H-6aF, H-6bF,
H-6aC, H-6bC, C-1A-O-CHa1, C-1A-O-CHa2, H-6bG, H-6aD, H-6bD, H-
5F, H-5D, H-2C, H-6aA, H-6bA, H-6aB, H-6bB, H-5B, H-5A), 3.15 (dd,
J = 2.7, 9.5 Hz, 1H, H-3C), 3.11 (m, 1H, H-5C), 2.93–2.84 (m, 2H,
CH2N3), 2.14, 2.12, 2.01, 1.99, 1.97, 1.88, 1.84 (s, 3H, OCH3), 1.29,
1.24 (s, 9H, t-BuCO), 1.41–1.19 (m, 4H, 2 ꢃ CH2), 1.14–1.07 (m,
2H, CH2). 13C NMR (126 MHz, CDCl3): 177.0, 176.8, 170.9, 170.5,
170.1, 170.0, 169.6, 169.3, 169.2, 138.6, 138.4, 138.3, 138.2,
138.1, 137.9, 137.5, 134.1, 133.6, 131.7, 131.6, 131.5, 131.3,
128.8, 128.4, 128.3, 128.2, 128.1, 128.0, 127.9, 127.8, 127.7,
127.6, 127.5, 127.3, 127.2, 126.4, 123.7, 123.6, 123.5, 123.4,
123.2, 123.1, 123.0, 100.9 (C-1F, JC-1-H-1 = 170.2 Hz), 100.7 (C-1C,
JC-1-H-1 = 155.5 Hz), 99.9 (C-1G, JC-1-H-1 = 173.1 Hz), 98.6 (C-1D, JC-1-
H-1 = 173.1 Hz), 98.1 (C-1B, JC-1-H-1 = 167.2 Hz), 97.9 (C-1E, JC-1-H-
1 = 164.3 Hz), 97.1 (C-1A, JC-1-H-1 = 167.2 Hz), 83.9, 78.6, 78.5, 75.1,
75.0, 74.8, 74.7, 74.6, 74.5, 74.0, 73.6, 73.5, 73.4, 73.1, 72.7, 71.9,
71.7, 71.6, 71.4, 71.0, 69.9, 69.5, 68.9, 68.6, 68.5, 68.2, 68.0, 65.8,
65.7, 62.6, 62.4, 61.6, 56.5, 55.8, 54.6, 51.1, 29.7, 28.7, 28.3, 27.3,
23.0, 21.1, 20.8, 20.6, 20.5. HRMS calcd for C158H174N6O48Na
[M+Na]+ 2946.1257, found 2946.1077.
Compound 31b: 1H NMR (500 MHz, CDCl3): 7.79 (m, 3H, Ar),
7.69–7.58 (m, 8H, Ar), 7.42 (m, 2H, Ar), 7.35–7.16 (m, 34H, Ar),
6.99 (m, 2H, Ar), 6.80–6.75 (m, 6H, Ar), 6.72 (m, 2H, Ar), 5.74
(dd, J = 9.0, 10.4 Hz, 1H, H-3E), 5.51 (t, J = 1.9 Hz, 1H, H-2D), 5.39
(dd, J = 3.3, 9.9 Hz, 1H, H-3G), 5.32 (d, J = 9.0 Hz, 1H, H-1E), 5.27
(7, J = 1.9 Hz, 1H, H-2G), 5.25 (d, J = 8.2 Hz, 1H, H-1A), 5.12 (t,
J = 9.5 Hz, 1H, H-4E), 5.08–5.04 (m, 4H, H-4F, H-3F, H-1F, H-1D),
4.95–4.86 (m, 4H, H-1B, 3 ꢃ CHBn), 4.81–4.62 (m, 7H, H-1G,
6 ꢃ CHBn), 4.50–4.36 (m, 11H, H-1C, H-2E, 9 ꢃ CHBn), 4.28–4.06
(m, 8H, H-2A, H-2B, H-3A, H-3B, H-4A, H-4B, H-6aE, H-2F), 4.00–
3.92 (m, 7H, H-6bE, H-6aG, H-4C, H-4G, H-4D, H-5D, H-3D), 3.84
(m, 2H, H-6aC, H-5G), 3.75–3.47 (m, 13H, H-6bG, H-6aF, H-6bF, H-
6aD, H-6aD, H-6bC, H-6aB, H-6aA, H-6bA, H-5F, H-5E, H-2C, C-1A-O-
CHa1), 3.41 (dd, J = 4.0, 10.8 Hz, 1H, H-6bB), 3.32–3.25 (m, 4H, C-
1A-O-CHa2, H-5B, H-5A, H-3C), 3.16 (m, 1H, H-5C), 2.94–2.83 (m,
2H, CH2N3), 2.16, 2.10, 2.06, 2.02, 2.00, 1.99, 1.96, 1.93, 1.86 (s,
3H, OCH3), 1.42–1.27 (m, 4H, 2 ꢃ CH2), 1.12–1.06 (m, 2H, CH2).
13C NMR from HSQC experiment (500 MHz, D2O) d (only anomeric
carbons): 101.0 (C-1C, JC-1-H-1 = 155.5 Hz), 98.0 (C-1B, JC-1-H-
1 = 161.4 Hz), 97.8 (C-1F, C-1D, JC-1-H-1 = 173.1 Hz), 97.1 (C-1A, JC-1-
H-1 = 167.2 Hz), 97.0 (C-1G, JC-1-H-1 = 176.0 Hz), 96.5 (C-1E, JC-1-H-
1 = 167.2 Hz). LRMS calcd for C152H162N6O48Na [M+NH4]2+
1437.56, found 1437.47.
Compound 32b: ½a D20
ꢂ
+4.8 (c 0.5, CH2Cl2). 1H NMR (500 MHz,
CDCl3): 7.80 (m, 3H, Ar), 7.69–7.59 (m, 8H, Ar), 7.42 (m, 2H, Ar),
7.35–7.16 (m, 35H, Ar), 6.99 (m, 2H, Ar), 6.83–6.79 (m, 5H, Ar),
6.74 (m, 2H, Ar), 5.73 (dd, J = 9.5, 10.4 Hz, 1H, H-3E), 5.49 (t,
J = 2.1 Hz, 1H, H-2D), 5.41 (dd, J = 3.3, 9.9 Hz, 1H, H-3G), 5.35 (d,
J = 8.5 Hz, 1H, H-1E), 5.26 (d, J = 8.1 Hz, 1H, H-1A), 5.22 (t,
J = 2.1 Hz, 1H, H-2G), 5.14 (t, J = 9.5 Hz, 1H, H-4E), 5.08 (m, 2H, H-
4F, H-3F), 5.01, 4.99 (d, J = 1.4 Hz, 2H, H-1F, H-1D), 4.94 (m, 2H, H-
1B, CHBn), 4.89–4.81 (m, 3H, 3 ꢃ CHBn), 4.73 (m, 2H, 2 ꢃ CHBn),
4.66 (m, 3H, H-1G, 2 ꢃ CHBn), 4.58 (d, J = 12.0 Hz, CHBn), 4.52–
4.38 (m, 11H, H-1C, H-2E, 9 ꢃ CHBn), 4.29 (m, 2H, H-2F, H-6aE),
4.20–4.11 (m, 5H, H-2A, H-2B, H-3A, H-3B, H-4B), 4.06–3.84 (m,
10H, H-6bE, H-6aG, H-6aC, H-4C, H-4G, H-5G, H-4D, H-5D, H-4A, H-
3D), 3.72–3.44 (m, 13H, H-6bG, H-6aF, H-6bF, H-6aD, H-6bD, H-
6aA, H-6aB, H-6bC, H-6aB, H-5F, H-5E, H-2C, C-1A-O-CHa1), 3.40
(dd, J = 4.0, 10.8 Hz, 1H, H-6bB), 3.33–3.24 (m, 4H, C-1A-O-CHa2,
H-5B, H-5A, H-3C), 3.15 (m, 1H, H-5C), 2.93–2.83 (m, 2H, CH2N3),
2.14, 2.10, 2.05, 2.02, 2.00, 1.94, 1.87, (s, 3H, OCH3), 1.21, 1.14 (s,
9H, t-BuCO), 1.43–1.06 (m, 6H, 3 ꢃ CH2). 13C NMR (126 MHz,
CDCl3): 176.8, 176.6, 170.8, 170.5, 170.4, 170.1, 170.0, 169.4,
169.2, 138.8, 138.7, 138.6, 138.4, 138.2, 137.9, 137.4, 134.2,
133.6, 131.8, 131.7, 131.5, 131.4, 130.9, 128.6, 128.4, 128.3,
128.2, 128.1, 128.0, 127.8, 127.7, 127.5, 127.3, 123.5, 123.5,
123.1, 123.0, 101.3 (C-1C, JC-1-H-1 = 155.5 Hz), 98.1 (C-1F, C-1D, JC-
1-H-1 = 173.1 Hz), 98.0 (C-1B, JC-1-H-1 = 164.3 Hz), 97.5 (C-1G, JC-1-H-
1 = 173.1 Hz), 97.2 (C-1A, JC-1-H-1 = 167.3 Hz), 96.6 (C-1E, JC-1-H-
1 = 164.3 Hz), 81.6, 79.0, 78.4, 76.1, 75.1, 74.9, 74.7, 74.6, 74.4,
74.3, 74.1, 74.0, 73.4, 73.3, 72.7, 72.6, 72.1, 71.7, 71.6, 70.9, 70.6,
69.8, 69.5, 68.8, 68.7, 68.6, 68.5, 68.2, 65.8, 65.5, 65.4, 62.7, 61.7,
56.5, 55.7, 54.4, 51.4, 51.1, 28.6, 28.3, 27.2, 23.0, 21.1, 20.8, 20.7,
3.5.4. 5-Azidopentyl[O-3,4,6-tri-O-acetyl-2-deoxy-2-
phthalimido-b-
mannopyranosyl]-(1?3)-[2-O-acetyl-3,4,6-tri-O-benzyl-
mannopyranosyl)-(1?6)-2,3-di-O-pivaloyl-4-O-benzyl-1-
mannopyranosyl]-(1?4)-2-O-benzyl– -mannopyranosyl-
(1?4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido–
glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-
phthalimido– -glucopyranoside (32a) and 5-Azidopentyl[O-
3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-b- -glucopyranosyl-
(1?2)-3,4,6-tri-O-acetyl- -mannopyranosyl]-(1?3)-[2-O-
acetyl-3,4,6-tri-O-benzyl-
O-pivaloyl-4-O-benzyl-1-
benzyl–
phthalimido–
deoxy-2-phthalimido–
To a stirred solution of donor 10 (35 mg, 33.1
(56 mg, 27.6 mol) with activated molecular sieves 3 Å in dry
CH2Cl2 (2.0 mL), TMSOTf (0.24 L, 1.3 mol) was added at 0 °C.
D-glucopyranosyl-(1?2)-3,4,6-tri-O-acetyl-a-D-
a-D-
a-D-
D
D-
D
D
a
a
-D
-
D
-mannopyranosyl)-(1?6)-2,3-di-
a
-D-mannopyranosyl]-(1?6)-2-O-
D
-mannopyranosyl-(1?4)-3,6-di-O-benzyl-2-deoxy-2-
-glucopyranosyl-(1?4)-3,6-di-O-benzyl-2-
-glucopyranoside (32b)
D
D
lmol), acceptor 2
l
l
l
20.6, 20.5, 20.4. HRMS calcd for
2946.1257, found 2946.1111.
C
158H174N6O48Na [M+Na]+
The reaction mixture was stirred for 2 h at room temperature.
The crude product was purified by preparative TLC (hexane/AcOEt,
1/2) to give a 1/1 mixture of two different compounds (32a and
32b) both of them as white foam (15 mg of 32a, 15 mg of 32b,
37% global yield).
3.6. General procedure for deprotection
Compound 32a: ½a D20
ꢂ
+4.7 (c 0.50, CH2Cl2). 1H NMR (500 MHz,
CDCl3): 7.88–7.49 (m, 10H, Ar), 7.39–7.14 (m, 37H, Ar), 7.03 (m,
The corresponding N-glycan (1 equiv) and ethylenediamine
(1.2 equiv) were dissolved in nBuOH and the reaction mixture