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G. O’Mahony et al. / Tetrahedron 63 (2007) 6901–6908
(400 MHz, CD3OD) 8.21 (1H, s), 8.12 (1H, s), 7.38–7.27
(5H, m), 5.90 (1H, d, J¼4.0 Hz), 5.22–5.17 (1H, m), 5.07–
5.04 (1H, m), 5.10 (1H, d, J¼12.5 Hz), 5.02 (1H, d,
J¼12.8 Hz), 4.10–4.02 (4H, m), 2.10–2.00 (1H, m), 1.17–
1.00 (28H, m), 0.89 (3H, d, J¼7.0 Hz), 0.82 (3H, d,
J¼7.0 Hz); dC (100 MHz, CD3OD) 156.0, 152.5, 140.5,
128.2, 127.8, 127.6, 88.3, 83.8, 70.2, 62.4, 66.5, 60.6,
55.1, 30.5, 18.5, 16.8, 16.6, 16.5, 16.4, 16.24, 16.19, 16.1,
13.5, 13.1, 12.8, 12.5; HRMS-FAB m/z [M+H+] calcd for
C35H55N7O7Si2: 742.378; found: 742.370. Anal. Calcd for
C35H55N7O7Si2: C, 56.65; H, 7.47; N, 13.21. Found: C,
56.68; H, 7.43; N, 13.18.
m); dC (100 MHz, CDCl3) 175.3, 173.2, 156.3, 156.2,
153.1, 148.7, 139.9, 136.0, 128.8, 128.5, 128.4, 119.5,
89.0, 84.1, 71.0, 67.6, 63.2, 56.9, 51.9, 37.0, 17.7, 17.6, 17.5,
17.4, 17.3, 17.22, 17.16, 13.3, 13.2, 12.89, 12.86; HRMS-
FAB m/z [M+H+] calcd for C34H52N8O8Si2: 757.345; found:
757.352. Anal. Calcd for C34H52N8O8Si2: C, 53.95; H, 6.92;
N, 14.80. Found: C, 53.91; H, 7.02; N, 14.71.
4.2.5. 20-(N-a-Benzyloxycarbonyl-L-phenylalaninyl)-
amino-20-deoxy-30,50-O-(tetraisopropyldisiloxane-1,3-
diyl)-adenosine (6e). Using general procedure A, 215 mg of
5b afforded 250 mg (75%) of 6e as a white solid, [a]2D0 ꢁ18.0
(c 0.02, CHCl3); nmax (KBr)/cmꢁ1 3400, 2944, 2866, 2359,
1715, 1645, 1600, 1498, 1464, 1455, 1331, 1296, 1248,
1214, 1142, 1037, 918, 885, 862, 745, 697, 648, 604, 458,
418; dH (400 MHz, CDCl3) 8.17 (1H, s), 7.95 (1H, s),
7.34–7.09 (10H, m), 5.89 (1H, d, J¼3.6 Hz), 5.28 (1H, m),
5.16 (1H, d, J¼12.5 Hz), 5.02 (1H, d, J¼12.5 Hz), 4.53
(1H, m), 4.02–3.97 (3H, m), 3.11 (1H, m, J¼7.3, 13.6 Hz,
CHCHHPh), 2.98 (1H, dd, J¼7.3, 13.6 Hz, CHCHHPh),
1.16–1.03 (28H, m); dC (100 MHz, CDCl3) 172.4, 156.4,
155.7, 152.6, 149.3, 140.2, 136.3, 129.2, 128.7, 128.6, 128.1,
127.0, 125.3, 119.8, 87.8, 83.8, 70.5, 67.0, 62.8, 56.5, 56.0,
38.0, 17.5, 17.4, 17.3, 17.2, 17.1, 17.0, 13.2, 13.1, 12.8, 12.6;
HRMS-FAB m/z [M+H+] calcd for C39H55N7O7Si2:
790.370; found: 790.376; Anal. Calcd for C39H55N7O7Si2:
C, 59.4; H, 6.9; N, 12.4. Found: C, 59.5; H, 6.9; N, 12.4.
4.2.2. 20-(N-a-Benzyloxycarbonyl-L-isoleucinyl)-amino-
20-deoxy-30,50-O-(tetraisopropyldisiloxane-1,3-diyl)-
adenosine (6b). Using general procedure A, 150 mg of 5b
afforded 149 mg (67%) of 6b as a white solid, [a]2D0 ꢁ29.5
(c 0.005, CHCl3); nmax (KBr)/cmꢁ1 3417, 2946, 2868,
2365, 1712, 1667, 1640, 1597, 1502, 1466, 1248, 1124,
1085, 1038, 885, 698; dH (400 MHz, CD3OD) 8.12 (1H, s),
8.03 (1H, s), 7.28–7.14 (5H, m), 5.81 (1H, d, J¼4.0 Hz),
5.20–5.03 (3H, m), 5.10 (1H, d, J¼12.5 Hz), 5.01 (1H, d,
J¼12.4 Hz), 4.12–4.00 (5H, m), 1.73–1.62 (1H, m), 1.24–
1.13 (1H, m), 1.06–0.84 (29H, m), 0.75 (3H, d, J¼7.0 Hz),
0.67 (3H, t, J¼7.4 Hz); dC (100 MHz, CD3OD) 173.1,
157.3, 156.0, 152.5, 149.0, 140.5, 136.7, 128.2, 127.8,
127.6, 119.2, 88.0, 84.0, 70.3, 66.5, 62.5, 59.9, 55.1, 36.9,
24.3, 16.7, 16.5, 16.4, 16.3, 16.2, 16.1, 14.7, 13.2, 13.1,
12.9, 12.4, 10.3; HRMS-FAB m/z [M+H+] calcd for
C36H57N7O7Si2: 756.394; found: 756.395; Anal. Calcd for
C36H57N7O7Si2: C, 57.2; H, 7.6; N, 13.0. Found: C, 57.2;
H, 7.6; N, 12.8.
4.2.6. 20-(N-a-Benzyloxycarbonyl-L-prolinyl)-amino-20-
deoxy-30,50-O-(tetraisopropyldisiloxane-1,3-diyl)-adeno-
sine (6f). Using general procedure A, 222 mg of 5b afforded
245 mg (76%) 6f as a white solid, [a]2D0 ꢁ47.0 (c 0.01,
CHCl3); nmax (KBr)/cmꢁ1 3394, 2944, 2867, 2726, 1694,
1599, 1499, 1465, 1416, 1332, 1299, 1248, 1206, 1119,
1090, 919, 885, 863, 824, 772, 696, 647, 607, 451, 418;
dH (400 MHz, CDCl3) 8.28 (1H, s), 8.11 (1H, s), 8.06 (1H,
s), 8.05 (1H, s), 7.35–7.21 (5H, m), 5.88 (1H, s), 5.77 (1H,
d, J¼9.0 Hz), 4.96–5.09 (7H, m), 4.78 (1H, d, J¼13.2 Hz),
4.30–4.36 (2H, m), 3.92–4.00 (6H, m), 3.34–3.42 (4H, m),
2.07–2.18 (1H, m), 1.79–1.91 (6H, m) 0.91–1.15 (56H,
m); dC (100 MHz, CDCl3) 173.0, 156.0, 155.8, 152.7,
149.3, 140.3, 136.4, 128.5, 128.2, 127.8, 120.1, 88.3, 83.6,
70.5, 67.3, 62.8, 60.6, 56.5, 47.0, 28.7, 24.6, 17.5, 17.4,
17.2, 17.1, 13.2, 12.8, 12.6; HRMS-FAB m/z [M+H+] calcd
for C35H53N7O7Si2: 740.355; found: 740.362.
4.2.3. 20-(N-a-Benzyloxycarbonyl-L-threoninyl)-amino-
20-deoxy-30,50-O-(tetraisopropyldisiloxane-1,3-diyl)-
adenosine (6c). Using general procedure A, 150 mg of 5b
afforded 145 mg (67%) of 6c as a white solid, [a]2D0 ꢁ15.0
(c 0.01, CHCl3); nmax (KBr)/cmꢁ1 3334, 2947, 2862, 1648,
1499, 1248, 1040, 917, 882, 698, 605, 456; dH (400 MHz,
CD3OD) 8.19 (1H, s), 8.12 (1H, s), 7.40–7.24 (5H, m),
5.95 (1H, d, J¼3.7 Hz), 5.25 (1H, t, J¼7.0 Hz), 4.93–4.91
(1H, m), 4.18–4.00 (1H, m), 4.0–4.18 (6H, m); dC
(100 MHz, CD3OD) 172.3, 157.3, 156.0, 152.4, 148.9,
140.7, 136.6, 128.2, 127.8, 127.6, 119.3, 88.5, 83.7, 70.4,
66.9, 66.7, 62.5, 60.6, 55.6, 18.44, 16.6, 16.52, 16.49,
16.4, 16.24, 16.22, 16.1, 13.13, 13.07, 12.8, 12.5; HRMS-
FAB m/z [M+H+] calcd for C34H53N7O8Si2: 744.349; found:
744.357; Anal. Calcd for C34H53N7O8Si2: C, 54.9; H, 7.2; N,
13.2. Found: C, 54.8; H, 7.5; N, 13.5.
4.2.7. 20-(N-a-Acetyl-N-u-benzyloxycarbonyl-L-lysinyl)-
amino-20-deoxy-30,50-O-(tetraisopropyldisiloxane-1,3-
diyl)-adenosine (6g). Using general procedure A, 150 mg of
5b afforded 187 mg (79%) 6g as a white solid, [a]2D0 ꢁ43.6
(c 0.01, CH3OH); nmax (KBr)/cmꢁ1 1690, 1638, 1541, 1466,
1255, 1142, 1039, 884, 697, 604; dH (400 MHz, DMSO-
d6) 8.33 (1H, d, J¼7.7 Hz), 8.32 (1H, s), 8.07 (1H, s), 8.01
(1H, d, J¼8.0 Hz), 7.38–7.30 (7H, m), 7.24 (1H, t,
J¼5.5 Hz), 5.86 (1H, d, J¼2.6 Hz), 5.10–5.04 (2H, m),
5.00 (2H, s), 4.35 (1H, td, J¼8.8, 4.4 Hz), 4.02–3.89 (3H,
m), 2.94 (2H, br q, J¼6.3 Hz), 1.80 (3H, s), 1.69–1.59
(1H, m), 1.51–1.21 (5H, m), 1.06–0.97 (28H, m); dC
(100 MHz, DMSO-d6) 172.8, 169.7, 159.7, 156.6, 153.1,
149.3, 140.7, 137.9, 128.9, 128.3, 119.8, 88.0, 82.8, 70.0,
65.6, 62.2, 54.6, 53.0, 42.3, 40.3, 40.1, 39.9, 33.1, 29.8,
23.4, 23.0, 17.9, 17.8, 17.42, 17.39, 17.36, 13.3, 13.1,
12.7, 12.6; HRMS-TSI-TOF m/z [M+H+] calcd for
4.2.4. 20-(N-a-Benzyloxycarbonyl-L-asparaginyl)-amino-
20-deoxy-30,50-O-(tetraisopropyldisiloxane-1,3-diyl)-
adenosine (6d). Using general procedure A, 190 mg of 5b
afforded 201 mg (71%) of 6d as a white solid, [a]D20
ꢁ0.002 (c 0.01, CHCl3); nmax (KBr)/cmꢁ1 3410, 2945,
2867, 2362, 2341, 1653, 1600, 1507, 1468, 1421, 1331,
1297, 1250, 1212, 1145, 1039, 918, 885, 863, 825, 696,
603, 456, 421; dH (400 MHz, CDCl3) 8.24 (1H, s), 7.95
(1H, s), 7.67 (1H, d, J¼4.4 Hz), 7.42–7.30 (5H, m), 6.45
(1H, d, J¼8.4 Hz), 5.89 (1H, d, J¼4.0 Hz), 5.84 (2H, br s),
5.23–5.16 (2H, m), 5.06 (1H, d, J¼12.4 Hz), 4.85–4.77
(1H, m), 4.61–4.53 (1H, m), 4.10–3.99 (3H, m), 3.02–2.94
(1H, m), 2.52 (1H, dd, J¼15.8, 5.5 Hz), 1.19–0.98 (28H,