5800
D. Crich et al. / Tetrahedron 58 *2002) 5789±5801
126.8, 128.4, 128.6, 128.7, 128.9, 136.9, 140.0, 141.7, 155.3,
165.5; 31P NMR d: 24.09; ESIMS, m/z: 618 [M11]1.
11.4 Hz, 1H), 5.07±5.10 &m, 1H), 5.47 &d, J7.2 Hz, 1H),
6.45 &t, J6.5 Hz, 1H), 7.29±7.40 &m, 5H), 7.83 &d,
J7.2 Hz, 1H); 13C NMR d: 16.5, 30.1, 40.6, 64.6, 70.2,
74.2, 85.0, 86.6, 94.0, 128.3, 128.5, 129.0, 137.7, 142.2,
155.8, 165.8; 31P NMR d: 23.37; ESIHRMS, calcd for
C20H28NaN3O7P: 476.1563. Found: 476.1549 [M1Na]1.
6.9.6. 50-O-Benzyl-20-deoxy-30-O-diethylphosphoryl-40a-
-2-phenyl-2-methylpropylthiocarbonyl)cytidine -40). H
1
NMR &CDCl3) d: 1.33±1.36 &m, 6H), 1.62 &s, 6H), 2.24±
2.33 &m, 1H), 2.73±2.79 &m, 1H), 3.13 &d, J13.5 Hz, 1H),
3.29 &d, J13.5 Hz, 1H), 3.69 &d, J10.0 Hz, 1H), 3.99 &d,
J10.0 Hz, 1H), 4.04±4.16 &m, 4H), 4.49 &d, J11.0 Hz,
1H), 4.63 &d, J11.0 Hz, 1H), 5.22±5.28 &m, 1H), 5.39 &d,
J7.5 Hz, 1H), 6.71±6.76 &m, 1H), 7.21±7.42 &m, 10H),
7.88 &d, J7.5 Hz, 1H); 13C NMR &CDCl3) d: 16.5, 28.2,
28.6, 30.1, 38.7, 40.6, 42.4, 64.7, 72.6, 74.5, 79.2, 87.3,
94.2, 126.1, 126.7, 128.4, 128.5, 128.7, 129.0, 129.1,
137.2, 142.3, 147.7, 165.9, 198.8; 31P NMR &CDCl3) d:
24.06; HRMS calcd for C31H41N3O8PS: 646.2352. Found:
646.2353 [M1H]1.
1
For 45: H NMR d: 1.28±1.36 &m, 6H), 2.28±2.35 &m,
1H), 3.02±3.06 &m, 1H), 3.76 &dd, J10.5, 7.0 Hz, 1H),
3.83 &dd, J10.5, 3.5 Hz, 1H), 4.07±4.14 &m, 4H), 4.49±
4.52 &m, 1H), 4.59 &d, J12.0 Hz, 1H), 4.65 &d, J11.9 Hz,
1H), 5.10±5.15 &m, 1H), 5.72 &d, J7.4 Hz, 1H), 6.18 &t,
J6.5 Hz, 1H), 7.32±7.38 &m, 5H), 7.53 &d, J7.4 Hz, 1H);
13C NMR d: 16.5, 30.1, 41.6, 64.6, 69.0, 74.1, 82.9, 92.6,
94.0, 128.2, 138.1, 141.5, 155.8, 165.8; 31P NMR d: 23.18;
ESIHRMS, calcd for C20H28NaN3O7P: 476.1563. Found:
476.1559 [M1Na]1.
6.9.11.
50-O-Benzyl-20-deoxy-30-O-diethylphosphoryl-
1
6.9.7. 50-O-Benzyl-20-deoxy-30-O-diethylphosphoryl-40a-
adenosine -46 and 47). For 46: H NMR d: 1.36±1.39
&m, 6H), 2.74±2.76 &m, 1H), 2.86±2.90 &m, 1H), 3.76 &dd,
J10.5, 3.1 Hz, 1H), 3.80 &dd, J10.5, 3.2 Hz, 1H), 4.14±
4.20 &m, 4H), 4.46±4.48 &m, 1H), 4.59 &s, 2H), 5.20±5.23
&m, 1H), 5.66 &br, s, 2H), 6.57 &dd, J8.2, 5.9 Hz, 1H),
7.33±7.39 &m, 5H), 8.10 &s, 1H), 8.36 &s, 1H); 13C NMR
d: 16.6, 30.1, 40.1, 64.6, 70.4, 74.2, 79.1, 84.5, 85.3, 128.3,
128.5, 129.0, 137.7, 139.3, 150.2, 153.5, 155.7; 31P NMR d:
23.36; ESIHRMS, calcd for C21H29N5O6P: 478.1855.
1
-2-phenylethylthiocarbonyl)adenosine -41). H NMR d:
1.34±1.37 &m, 6H), 2.87±2.90 &m, 3H), 2.95±3.05 &m,
1H), 3.01±3.13 &m, 2H), 3.79 &d, J10.1 Hz, 1H), 4.05 &d,
J10.1 Hz, 1H), 4.12±4.16 &m, 4H), 4.59 &d, J11.7 Hz,
1H), 4.62 &d, J11.7 Hz, 1H), 5.37±5.40 &m, 1H), 5.85 &br,
s, 2H), 6.80 &dd, J8.6, 5.8 Hz, 1H), 7.23±7.39 &m, 10H),
8.11 &s, 1H), 8.36 &s, 1H); 13C NMR d: 16.6, 30.4, 37.4,
40.4, 64.8, 72.6, 74.6, 79.9, 85.1, 95.2, 95.3, 127.0, 128.0,
128.2, 128.5, 128.7, 128.8, 128.9, 129.0, 129.1, 137.1,
139.4, 140.3, 150.2, 153.6, 155.8; 31P NMR d: 24.06;
ESIMS, m/z: 642 [M11]1.
1
Found: 478.1852 [M1H]1. 47: H NMR d: 1.33±1.38 &m,
6H), 2.92±2.95 &m, 1H), 3.30±3.33 &m, 1H), 3.75 &dd,
J10.3, 6.8 Hz, 1H), 3.83 &dd, J10.3, 4.5 Hz, 1H),
4.12±4.17 &m, 4H), 4.57 &d, J12.0 Hz, 1H), 4.63 &d,
J12.0 Hz, 1H), 4.87±4.88 &m, 1H), 5.34±5.36 &m, 1H),
6.9.8. 50-O-Benzyl-20-deoxy-30-O-diethylphosphoryl-40a-
-2-phenyl-2-methylpropylthiocarbonyl)adenosine -42).
1H NMR &CDCl3) d: 1.34±1.38 &m, 6H), 1.40 &s, 6H),
2.82±2.87 &m, 1H), 2.93±3.01 &m, 1H), 3.13 &d, J
13.5 Hz, 1H), 3.34 &d, J13.5 Hz, 1H), 3.72 &d, J
10.3 Hz, 1H), 3.99 &d, J10.3 Hz, 1H), 4.09±4.16 &m,
4H), 4.56 &d, J11.8 Hz, 1H), 4.60 &d, J11.8 Hz, 1H),
5.33±5.36 &m, 1H), 5.64 &s, 2H), 6.72±6.75 &m, 1H),
7.20±7.23 &m, 1H), 7.29±7.39 &m, 9H), 8.10 &s, 1H), 8.35
&s, 1H); 13CNMR &CDCl3) d: 16.5, 16.6, 28.2, 28.5, 30.1,
31.3, 38.8, 40.3, 42.4, 51.3, 64.7, 72.7, 74.6, 79.6, 85.1,
95.4, 120.1, 126.1, 126.7, 128.2, 128.4, 128.7, 129.1,
137.1, 139.5, 147.7, 150.1, 153.6, 155.7, 198.7; 31P NMR
&CDCl3) d: 24.11; HRMS calcd for C32H41N5O7PS:
670.2464. Found: 670.2485 [M1H]1.
1
5.70 &br, s, 2H), 6.40 &t, J6.8 Hz, H), 7.29±7.36 &m,
5H), 7.89 &s, 1H), 8.33 &s, 1H); 13C NMR d: 16.6, 30.1,
39.4, 64.6, 68.6, 74.1, 78.5, 82.6, 85.4, 121.0, 128.2,
128.8, 138.1, 140.3, 149.9, 153.4, 155.8; 31P NMR d:
23.15; ESIHRMS, calcd for C21H28NaN5O6P: 500.1675.
Found: 500.1668 [M1Na]1.
6.9.12.
50-O-Benzyl-30,40-didehydro-20,30-dideoxycyti-
1
dine -49). H NMR d: 2.52±2.56 &m, 1H), 3.15±3.20 &m,
1H), 4.15 &s, 2H), 4.64 &s, 2H), 5.10 &s, 1H), 5.65 &d, J
7.4 Hz, 1H), 6.67 &dd, J9.0, 3.4 Hz, 1H), 7.34±7.51 &m,
5H), 7.52 &d, J7.4 Hz, 1H); 13C NMR d: 29.9, 38.1, 64.5,
73.2, 87.0, 94.2, 99.3, 127.9, 128.2, 128.7, 137.8, 141.0,
155.4, 165.3; ESIHRMS, calcd for C16H17NaN3O3:
322.1168. Found: 322.1162 [M1Na]1.
6.9.9. 50-O-Benzyl-20-deoxy-30-O-diethylphosphoryl-40a-
-phenylethylthiocarbonyl)guanosine -43). 1H NMR d:
1.28±1.40 &m, 6H), 2.07 &br, s, 2H), 2.84±3.12 &m, 4H),
3.80 &br, s, 1H), 4.00 &d, J10.1 Hz, 1H), 4.13±4.18 &m,
4H), 4.61 &s, 2H), 5.44 &s, 1H), 6.15 &br, s, 2H), 6.55±6.57
&m, 1H), 7.23±7.37 &m, 10H), 7.82 &s, 1H); 13C NMR d:
16.6, 36.0, 40.6, 64.8, 72.5, 74.5, 79.8, 84.9, 95.0, 100.6,
117.5, 127.0, 128.4, 128.6, 128.9, 129.0, 130.5, 136.3,
137.2, 140.0, 142.8, 151.9, 154.2, 159.5; 31P NMR d:
24.03; ESIMS, m/z: 680 [M1Na]1.
6.9.13. 50-O-Benzyl-30,40-didehydro-20,30-dideoxyguano-
sine -51). 1H NMR &CD3OD) d: 3.04±3.07 &m, 1H),
3.30±3.36 &m, 1H), 4.14 &s, 2H), 4.52 &d, J11.6 Hz, 1H),
4.56 &d, J11.8 Hz, 1H), 5.28 &s, 1H), 6.67 &dd, J9.3,
3.4 Hz, 1H), 7.27±7.35 &m, 5H), 7.85 &s, 1H); 13C NMR
&d6-DMSO) d: 64.6, 72.1, 76.3, 80.8, 83.4, 99.5, 117.3,
128.4, 128.6, 129.1, 135.0, 138.8, 151.7, 153.6, 155.1,
158.0, 159.3; ESIMS, m/z: 340 [M11]1.
6.9.14. 50-O-Benzyl-20,30-didehydro-20,30-dideoxycytidine
-52). H NMR d: 4.11 &s, 2H), 4.65 &s, 2H), 4.91 &s, 1H),
1
6.9.10.
50-O-Benzyl-20-deoxy-30-O-diethylphosphoryl-
1
cytidine -44 and 45). For 44: H NMR d: 1.29±1.42 &m,
6H), 2.19±2.23 &m, 1H), 2.68±2.71 &m, 1H), 3.77 &dd,
J10.5, 2.2 Hz, 1H), 3.85 &dd, J10.5, 2.2 Hz, 1H),
4.11±4.17 &m, 4H), 4.38 &d, J2.3 Hz, 1H), 4.54 &d, J
5.30 &s, 1H), 5.65 &d, J7.4 Hz, 1H), 6.18 &s, 1H), 7.35±7.49
&m, 6H), 7.49 &d, J7.3 Hz, 1H); 13C NMR d: 64.8, 73.5,
75.8, 81.1, 91.6, 93.9, 96.0, 102.7, 117.8, 128.1, 129.0,
140.6, 155.4, 165.3; ESIMS, m/z: 300 [M11]1.