Molecules 2009, 14
3348
J = 7.8 Hz, DMTrH-3’,5’), 7.18 (2H, d, J = 7.8 Hz, DMTrH-3”,5”), 6.77 (2H, d, J = 7.8 Hz, DMTrH-
2”,6”), 6.73 (2H, d, J = 7.8 Hz, DMTrH-2’,6’), 6.20 (1H, dd, J = 4.8, 7.8, H-1′), 4.57 (1H, q,
J = 5.9 Hz, H-3′), 3.93 (1H, m, H-4′), 3.71 and 3.70 (3H each, s, OCH3), 3.30 (1H, dd, J = 7.2,10 Hz,
H-5”), 3.21 (1H, ddd, J = 5.4, 7.2, 13.4 Hz, H-2′′), 3.15 (1H, dd, J = 2.8,10 Hz, H-5′), 3.03 and 2.98
13
(3H each, s, N(CH3)2), and 2.20 (1H, ddd, J = 6.0,8.0,13.4 Hz, H-2′); C-NMR (DMSO-d6): δ ppm
157.9, 157.9, 157.6, 157.5, 156.4, 150.5, 147.5, 144.9, 135.7, 135.6, 129.6, 129.4, 129.3, 129.0, 127.6,
127.6, 126.5, 120.3, 112.9, 112.9, 85.7, 85.2, 84.1, 70.8, 64.0, 54.9, 54.9, 40.7, 37.4, 34.6, and 34.2;
UV: (MeCN) max (log ) 233 (4.63) and 322 (4.44); MS: m/z for MW 744.80, calculated MH+ 745.80,
found 745.767 (M+Na)+, and 1511.0 (2M+Na)+.
5′-O-(DMTr)-N2-(N,N-dimethylformamidine)-C8-(4-(TBS-O-methyl)phenyl)-2′-deoxyguanosine (5d):
Yield 41%; 1H-NMR (DMSO-d6): δ ppm 11.41 (1H, s, NH), 8.31 (1H, s, HC=N), 7.74 and 7.46 (4H,
d, J = 8.4, ArH-2,6 and ArH-3,5), 7.33 (2H, d, J = 8.4 Hz, DMTrH-2,6), 7.24 (3H, m, DMTrH-3,4,5),
7.21 (2H, d, J = 8.5 Hz, DMTrH-3’,5’), 7.18 (2H, d, J = 8.5 Hz, DMTrH-3”,5”), 6.77 (2H, d, J = 8.5
Hz, DMTrH-2’,6’), 6.73 (2H, d, J = 8.5 Hz, DMTrH-2”,6”), 6.17 (1H, dd, J = 5.4,7.8 Hz, H-1′), 5.28
(1H, d, J = 5.6 Hz, 3′-OH), 4.81 (2H, s, CH2), 4.57 (1H, p, J = 5.1 Hz, H-3′), 3.93 (1H, m, H-4′), 3.71
and 3.70 (3H each, s, OCH3), 3.32 (1H, dd, J = 6.3, 10.2 Hz, H-5’or 5′′), 3.21 (1H, p, J = 6.3 Hz, H-
2′′), 3.15 (2H, dd, J = 2.8, 10.2 Hz, H-5′ or 5′′), 3.03 and 2.98 (3H each, s, N(CH3)2), 2.18 (1H, ddd, J
= 5.8,8,13.7, H-2′), 0.94 (9H, s, t-butyl), and 0.12 (6H, s, dimethylsilyl); 13C-NMR (DMSO-d6): δ ppm
157.9, 157.9, 157.5, 156.3, 150.4, 148.2, 144.9, 142.6, 135.7, 135.6, 129.6, 129.4, 129.1, 128.9, 127.6,
127.6, 126.5, 126.0, 120.0, 113.1, 112.9, 112.9, 85.7, 85.2, 84.0, 70.9, 64.0, 63.9, 54.9, 54.9, 40.7,
37.4, 34.6, 25.8, 18.0, and -5.4; UV: (MeCN) max (log ) 231 (4.60) 316 (4.36); MS: m/z for MW
845.08, calculated MH+ 846.08, found 845, 867 (M+Na)+, and 1712 (2M+Na)+.
5′-O-(DMTr)-N2-(N,N-dimethylformamidine)-C8-(4-methoxymethylphenyl)-2′-deoxyguanosine (5e):
Yield 55%; 1H-NMR (DMSO-d6): δ ppm 11.42 (1H, s, NH), 8.31 (1H, s, HC=N), 7.74 (2H, d, J = 8.4
Hz, ArH-2,6 or 3,5), 7.46 (2H, d, J = 8.4, ArH-2,6 or 3,5), 7.32 (2H, d, J =8.9 Hz, DMTrH-2,6), 7.19
(2H, d, J = 8.7 Hz, DMTrH-3’,5’), 7.18 (2H, d, J = 8.7 Hz, DMTrH-3”,5”), 7.14-7.18 (3H, m, ArH-3,4
5), 6.77 (2H, d, J = 8.7 Hz, DMTrH-2”,6”), 6.73 (2H, d, J = 8.7 Hz, DMTrH-2’,6’), 6.17 (1H, dd, J =
3.0, 6.6 Hz, H-1′), 5.28 (1H, d, J = 4.9 Hz, 3′-OH), 4.57 (1H, p, 5.5 Hz, H-3′), 4.50 (2H, s, CH2), 3.92
(1H, m, H-4′), 3.71 and 3.70 (3H each, s, OCH3), 3.35 (3H, s, CH3), 3.30 (1H, dd, J = 7,9.9 Hz, H-5′ or
5′′), 3.20 (1H, ddd, J = 5,6.8,13 Hz, H-2′′), 3.15 (1H, dd, J = 3, 9.9 Hz, H-5′ or 5′′), 3.03 and 2.98 (3H
13
each, s, N(CH3)2), and 2.18 (1H, ddd, 5.7, 8, 13.5 Hz, H-2′); C-NMR (DMSO-d6): δ ppm 157.9,
157.9, 157.5, 156.3, 150.4, 148.1, 144.9, 139.8, 135.7, 135.6, 129.6, 129.4, 129.1, 127.6, 127.6, 127.5,
126.5, 120.1, 112.9, 112.9, 85.7, 85.2, 84.0, 73.1, 70.9, 64.0, 57.7, 54.9, 54.9, 40.7, 37.4, and 34.6;
UV: (MeCN) max (log ) 231 (4.54) and 319 (4.37); MS: m/z for MW 744.85, calculated MH+ 745.85,
found 746, 768 (M+Na)+, 784 (M+K)+, and 1512 (2M+Na)+.
5'-O-(4,4'-Dimethoxytrityl)-N2-(N,N-dimethylformamidine)-C8-phenyl-2'-deoxyadenosine (10a): Yield
58%; IR (KBr) cm-1 3500-3130, 2940, 2600, 2500, 1670-1530, 1505, 1440, 1420, 1330, 1250, 1170,
1110, 1040; 1H-NMR (MeCN-d3) ppm 8.87 (1H, s, HCN), 8.20 (1H, s, H-2), 7.83 (2H, d, J = 7.3 Hz,
ArH-3,5), 7.55 (3H, m, ArH-2,6), 7.38 (2H, d, J = 7Hz DMTrH-2”,6”), 7.25 and 7.24 (4H, d, J = 8.8