CHEMISTRY & BIODIVERSITY – Vol. 8 (2011)
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6-Chloro-9-{[1-(2,3,4,6-tetra-O-acetyl-b-d-glucopyranosyl)-1H-1,2,3-triazol-4-yl]methyl}-2-({[1-
(2,3,4,6-tetra-O-acetyl-b-d-glucopyranosyl)-1H-1,2,3-triazol-4-yl]methyl}amino)-9H-purine (8). From 3
(207 mg, 1.0 mmol) and 6 (834 mg, 2.2 mmol). Click reaction and CC (AcOEt/PE 1:6 to 1:4) afforded 8
(1.058 g, 84%). Yellow powder. Rf (AcOEt/PE, 1:2) 0.65. [a]D ¼ ꢁ35.9 (c¼2.0, CH2Cl2). 1H-NMR
(400 MHz, CDCl3): 7.88 (s, 1 H); 7.83 (s, 2 H); 7.22 (t, J¼6.4, 1 H); 5.86 (d, J¼8.8, 2 H); 5.67 (d, J ¼ 6.4,
2 H); 5.46–5.38 (m, 2 H); 5.23 (t, J¼9.6, 2 H); 5.09 (d, J¼15.6, 2 H); 4.92 (d, J¼15.6, 2 H); 4.29 (dd, J¼
7.6, 12.8, 2 H); 4.15 (d, J¼12.4, 2 H); 4.00 (dd, J¼2.8, 10.0, 2 H); 2.07 (s, 6 H); 2.06 (s, 6 H); 2.03 (s, 6 H);
1.85 (s, 6 H). 13C-NMR (100 MHz, CDCl3): 202.4; 170.5; 169.9; 169.4; 168.9; 157.9; 152.5; 151.2; 145.2;
139.6; 124.8; 121.2; 92.8; 88.9; 85.7; 75.1; 72.6; 70.2; 67.7; 61.6; 42.3; 20.7; 20.6; 20.5; 20.2. HR-MS:
1014.2606 (C39H46ClN11NaOþ18 ; calc. 1014.2609).
Methyl 6-{4-[(2-Amino-6-chloro-9H-purin-9-yl)methyl]-1H-1,2,3-triazol-1-yl}-2,3,4-tri-O-benzyl-6-
deoxy-a-d-glucopyranoside (9). From 2 (207 mg, 1.0 mmol) and 4 (538 mg, 1.1 mmol). Click reaction
and CC (AcOEt/PE 1:6 to 1:4) afforded 9 (593 mg, 85%). Yellow powder. Rf (AcOEt/PE 1:2) 0.48.
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[a]D ¼ þ11.5 (c¼1.2, CH2Cl2). H-NMR (400 MHz, CDCl3): 7.93 (s, 1 H); 7.61 (s, 1 H); 7.35–7.30 (m,
15 H); 5.37 (br. s, 2 H); 5.11 (br. s, 2 H); 4.99 (d, J¼10.4, 1 H); 4.92 (d, J¼10.8, 1 H); 4.81 (d, J¼10.8,
1 H); 4.78 (d, J¼10.8, 1 H); 4.71 (d, J¼10.8, 1 H); 4.63 (d, J¼12.0, 1 H); 4.55–4.49 (m, 3 H); 4.00 (t, J¼
9.2, 1 H); 3.95–3.91 (m, 1 H); 3.40 (dd, J¼2.8, 9.6, 1 H); 3.14 (t, J¼9.6, 1 H); 3.11 (s, 3 H). 13C-NMR
(100 MHz, CDCl3): 159.3; 153.5; 151.3; 142.2; 141.9; 138.3; 137.9; 137.8; 128.6; 128.5; 128.4; 128.2; 128.0;
127.8; 125.0; 124.3; 98.0; 81.7; 79.9; 77.9; 75.8; 74.9; 73.4; 69.0; 55.2; 50.9; 38.6. HR-MS: 719.2478
(C36H37ClN8NaOþ5 ; calc. 719.2473).
Methyl 6-{4-[(2-Amino-6-chloro-9H-purin-9-yl)methyl]-1H-1,2,3-triazol-1-yl}-2,3,4-tri-O-benzyl-6-
deoxy-a-d-galactopyranoside (10). From 2 (207 mg, 1.0 mmol) and 5 (538 mg, 1.1 mmol). Click reaction
and CC (AcOEt/PE 1:6 to 1:4) afforded 10 (599 mg, 86%). Yellow powder. Rf (AcOEt/PE 1:2) 0.52.
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[a]D ¼ þ40.4 (c¼2.8, CH2Cl2). H-NMR (400 MHz, CDCl3): 7.85 (s, 1 H); 7.54 (s, 1 H); 7.40–7.26 (m,
15 H); 5.30 (br. s, 4 H); 5.02 (d, J¼11.6, 1 H); 4.89 (d, J¼11.6, 1 H); 4.82 (d, J¼12.0, 1 H); 4.73 (d, J¼
11.6, 1 H); 4.65 (d, J¼12.4, 1 H); 4.60 (d, J¼11.6, 1 H); 4.51 (d, J¼3.6, 1 H); 4.31 (dd, J¼9.6, 14.0, 1 H);
4.16 (dd, J¼2.4, 14.0, 1 H); 4.00 (dd, J¼3.6, 10.0, 1 H); 3.95–3.91 (m, 1 H); 3.90 (dd, J¼2.8, 12.8, 1 H);
3.82 (br. s, 1 H); 2.79 (s, 3 H). 13C-NMR (100 MHz, CDCl3): 159.1; 153.3; 151.4; 142.0; 141.6; 138.4; 138.2;
137.8; 128.6; 128.5; 128.5; 128.4; 128.2; 128.1; 127.8; 127.9; 127.6; 125.0; 124.3; 98.7; 78.6; 76.1; 75.0; 74.6;
73.9; 73.6; 69.3; 54.9; 51.4; 38.5. HR-MS: 697.2666 (C36H38ClN8Oþ5 ; calc. 697.2654).
6-Chloro-N,9-bis[(1-{[(2R,3R,4S,5R,6S)-3,4,5-tris(benzyloxy)-tetrahydro-6-methoxy-2H-pyran-2-
yl]methyl}-1H-1,2,3-triazol-4-yl)methyl]-9H-purin-2-amine (13). From 3 (207 mg, 1.0 mmol) and 4
(1.076 g, 2.2 mmol). Click reaction and CC (AcOEt/PE 1:6 to 1:4) afforded 13 (1.044 g, 85%). Yellow
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powder. Rf (AcOEt/PE 1:2) 0.42. [a]D ¼ ꢁ45.1 (c¼1.0, CH2Cl2). H-NMR (400 MHz, CDCl3): 7.81 (s,
1 H); 7.68 (br. s, 2 H); 7.35–7.27 (m, 30 H); 7.16 (t, J¼6.4, 1 H); 5.63 (d, J ¼ 6.4, 2 H); 4.97 (d, J¼10.8,
4 H); 4.96 (d, J¼8.0, 2 H); 4.90 (d, J¼10.8, 2 H); 4.80 (d, J¼10.4, 2 H); 4.72 (d, J¼10.0, 4 H); 4.61 (d,
J¼12.0, 2 H); 4.53 (dd, J¼2.8, 14.0, 4 H); 4.48 (dd, J¼6.0, 14.4, 2 H); 3.99 (t, J¼9.6, 2 H); 3.95–3.91 (m,
2 H); 3.39 (dd, J¼3.6, 9.6, 2 H); 3.15 (t, J¼9.2, 2 H); 3.13 (s, 6 H). 13C-NMR (100 MHz, CDCl3): 202.3;
160.9; 158.1; 152.8; 145.1; 138.4; 137.9; 137.8; 136.7; 128.5; 128.2; 128.1; 128.0; 127.8; 123.8; 98.0; 92.9;
88.5; 81.8; 80.0; 78.0; 75.8; 75.0; 73.4; 69.2; 55.2; 50.7; 42.5. HR-MS: 1246.4877 (C67H70ClN11NaOþ10 ; calc.
1246.4893).
6-Chloro-N,9-bis[(1-{[(2R,3S,4S,5R,6S)-3,4,5-tris(benzyloxy)-tetrahydro-6-methoxy-2H-pyran-2-
yl]methyl}-1H-1,2,3-triazol-4-yl)methyl]-9H-purin-2-amine (14). From 3 (207 mg, 1.0 mmol) and 5
(1.076 g, 2.2 mmol). Click reaction and CC (AcOEt/PE 1:6 to 1:4) afforded 14 (1.058 g, 87%). Yellow
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powder. Rf (AcOEt/PE 1:2) 0.43. [a]D ¼ þ32.4 (c¼1.0, CH2Cl2). H-NMR (400 MHz, CDCl3): 7.83 (s,
1 H); 7.52 (br. s, 2 H); 7.32–7.24 (m, 30 H); 7.09 (t, J¼6.8, 1 H); 5.60 (d, J¼6.8, 2 H); 5.01 (d, J¼11.6,
2 H); 4.90 (br. s, 2 H); 4.87 (d, J¼11.6, 2 H); 4.80 (d, J¼12.0, 2 H); 4.72 (d, J¼11.6, 2 H); 4.64 (d, J¼
12.0, 2 H); 4.59 (d, J¼11.6, 2 H); 4.53 (br. s, 2 H); 4.29 (dd, J¼9.2, 14.0, 2 H); 4.18 (dd, J¼3.2, 14.0, 2 H);
3.99 (dd, J¼3.2, 10.0, 2 H); 3.96 (dd, J¼2.8, 9.2, 2 H); 3.89 (dd, J¼2.8, 10.0, 2 H); 3.82 (br. s, 2 H); 2.85
(s, 6 H). 13C-NMR (100 MHz, CDCl3): 202.2; 157.7; 152.3; 151.0; 144.1; 139.4; 138.4; 138.2; 137.9; 128.5;
128.4; 128.1; 127.8; 127.7; 127.6; 124.3; 98.6; 92.5; 88.9; 78.7; 76.1; 75.0; 74.6; 73.8; 73.6; 69.4; 54.9; 51.2;
42.5. HR-MS: 1246.4893 (C67H70ClN11NaOþ10 ; calc. 1246.4893).