The Journal of Organic Chemistry
(m, 1H), 1.67-1.57 (m, 2H), 1.22-1.15 (m, 1H), 1.01-0.94 (m,
Page 10 of 14
1H). 13C{1H} NMR (75 MHz, CDCl3) δ 162.0, 159.9, 158.9,
158.6, 152.1, 144.3, 144.1, 135.4, 135.3, 130.2, 130.2, 130.0,
128.2, 127.9, 127.0, 127.0, 126.7, 114.0, 113.6, 113.2, 94.4,
86.9, 86.7, 85.4, 82.0 (d, 2JPC = 9.3 Hz), 71.2 (d, 2JPC = 12.3 Hz),
67.7, 67.4 (d, 3JPC = 3.1 Hz), 61.8, 55.3, 55.2, 55.1, 53.1, 50.2,
47.2 (d, 2JPC = 34.6 Hz), 41.0, 28.0, 25.9 (d, 3JPC = 3.7 Hz), 20.7.
31P{1H} NMR (162 MHz, CDCl3) δ 156.7. FAB-HRMS: Calcd.
for C51H54N4O11P+ [M+Na]+; [M+H]+; 929.3521. Found;
929.3528.
1
2
3
4
5
6
7
8
Sp-dAMCbz monomer: (Sp)-17
The same procedure as the synthesis of (Rp)-15 was ap-
plied for compound 13 (1.05 g, 1.46 mmol) and (4R, 5S)-14
(3.67 mmol). The crude product was purified by silica gel
column chromatography (NH-silica gel, toluene-AcOEt (8:2,
v/v) containing 0.1% triethylamine) to afford (Sp)-17 (0.67
g, 0.70 mmol, 48%).
9
1H NMR (400 MHz, CDCl3) δ 8.67 (s, 1H), 8.33-8.26 (br, 1H),
8.12 (s, 1H), 7.41-7.35 (m, 4H), 7.30-7.12 (m, 9H), 6.91-6.74
(m, 8H), 6.45 (t, J = 6.4 Hz, 1H), 5.71 (d, J = 6.4 Hz, 1H), 5.22
(s, 2H), 5.06-5.00 (m, 1H), 4.34-4.31 (m, 1H), 3.91-3.76 (s,
13H), 3.62-3.52 (m, 1H), 3.48-3.34 (m, 2H), 3.22-3.13 (m,
1H), 2.94-2.88 (m, 1H), 2.63-2.58 (m, 1H), 1.69-1.58 (m, 2H),
1.26-1.19 (m, 1H), 1.06-0.98 (m, 1H). 13C{1H} NMR (75 MHz,
CDCl3) δ 159.8, 158.9, 158.4, 152.6, 150.9, 150.8, 149.3,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Sp-dCMCbz monomer: (Sp)-16
The same procedure as the synthesis of (Rp)-15 was ap-
plied for compound 10 (1.01 g, 1.46 mmol) and (4R, 5S)-14
(3.67 mmol). The crude product was purified by silica gel
column chromatography (NH-silica gel, toluene-AcOEt (7:3,
v/v) containing 0.1% triethylamine) to afford (Sp)-16 (0.55
g, 0.59 mmol, 40%).
3
144.4, 141.3, 135.6, 135.5, 130.5, 130.1 (d, JPC = 3.8 Hz),
130.0, 128.1, 127.8, 127.5, 127.0, 126.8, 126.7, 122.4, 113.9,
113.7, 113.6, 113.1, 86.5, 85.7, 85.6, 84.6, 82.2 (d, 2JPC = 9.9
Hz), 73.0 (d, 2JPC = 11.8 Hz), 67.5, 67.4 (d, 3JPC = 3.1 Hz), 62.9,
55.2, 55.2, 55.1, 53.0, 47.2 (d, 2JPC = 34.0 Hz), 39.6, 28.0, 26.0
(d, 3JPC = 3.1 Hz), 20.7. 31P{1H} NMR (162 MHz, CDCl3) δ155.4.
FAB-HRMS: Calcd. for C52H54N6O10P+ [M+Na]+; 953.3634.
Found; 953.3643.
1H NMR (400 MHz, CDCl3) δ 8.36 (d, J = 7.6 Hz, 1H), 7.43-
7.16 (m, 14H), 6.94-6.84 (m, 9H), 6.24-6.20 (m, 1H), 5.68 (d,
J = 6.4 Hz, 1H), 5.13 (s, 2H), 4.90-4.83 (m, 1H), 4.19-4.15 (m,
1H), 3.87-3.76 (m, 13H), 3.57-3.43 (m, 3H), 3.22-3.13 (m,
1H), 2.69-2.63 (m, 1H), 2.41-2.32 (m, 1H), 1.69-1.60 (m, 2H),
1.26-1.17 (m, 1H), 1.04-0.95 (m, 1H). 13C{1H} NMR (75 MHz,
CDCl3) δ162.0, 159.8, 158.9, 158.6, 158.6, 154.8, 152.1,
144.3, 144.0, 135.4, 135.2, 130.2, 130.1, 130.0, 129.9 (d, 3JPC
= 3.7 Hz), 128.1, 127.9, 127.0, 126.7, 114.0, 113.6, 113.6,
113.2, 94.4, 86.9, 86.5, 85.2, 85.1, 82.0 (d, 2JPC = 9.3 Hz), 70.3
(d, 2JPC = 11.1 Hz), 67.6, 67.4 (d, 3JPC = 3.8 Hz), 61.4, 55.2, 55.2,
55.1, 47.2 (d, 2JPC = 34.7 Hz), 41.0, 28.0, 25.9 (d, 3JPC = 3.7 Hz).
31P{1H} NMR (162 MHz, CDCl3) δ 156.0. FAB-HRMS: Calcd.
for C51H53N4NaO11P+ [M+Na]+; 951.3341. Found; 951.3349.
Rp-dGtse monomer: (Rp)-18
The same procedure as the synthesis of (Rp)-15 was ap-
plied for O6-tse-5'-O-DMTr-2'-deoxyguanosine (0.67 g, 1.00
mmol) and (4S, 5R)-14 (3.95 mmol), except for the reaction
was conducted at -78 °C. The crude product was purified by
silica gel column chromatography (NH-silica gel, toluene-
AcOEt (9:1, v/v) containing 0.1% triethylamine) to afford
(Rp)-18 (0.34 g, 0.38 mmol, 37%).
Rp-dAMCbz monomer: (Rp)-17
1H NMR (400 MHz, CDCl3) δ 7.69 (s, 1H), 7.43-7.13 (m, 11H),
6.92-6.72 (m, 6H), 6.32 (t, J = 6.0 Hz, 1H), 5.75 (d, J = 6.4 Hz,
1H), 5.08-5.00 (br, 1H), 4.65-4.53 (m, 4H), 4.26 (s, 1H), 3.88-
3.70 (m, 9H), 3.64-3.53 (m, 1H), 3.42-3.29 (m, 2H), 3.20-
3.13 (m, 2H), 3.00-2.90 (m, 1H), 2.57-2.50 (m, 1H), 1.68-
1.55 (m, 2H), 1.26-1.12 (m, 3H), 1.03-0.96 (m, 1H), 0.08 (s,
9H). 13C{1H} NMR (75 MHz, CDCl3) δ 161.3, 159.1, 158.9,
158.4, 153.4, 144.7, 137.6, 135.8, 135.8, 130.3 (d, 3JPC = 3.8
Hz), 130.1, 130.0, 128.1, 127.8, 127.3, 127.0, 126.7, 126.7,
116.3, 114.2, 113.7, 113.6, 113.1, 86.3, 85.4, 84.1, 82.2 (d,
2JPC = 9.3 Hz), 81.8, 73.8 (d, 2JPC = 11.8 Hz), 67.6 (d, 3JPC = 3.7
Hz), 67.0, 64.8, 63.2, 55.3, 55.2, 55.1, 53.1, 50.3, 47.9, 47.2 (d,
2JPC = 34.1 Hz), 45.7, 39.1, 31.0, 29.7, 28.1, 26.5, 26.0 (d, 3JPC
= 3.7 Hz) , 20.7, 17.5, -1.4. 31P{1H} NMR (162 MHz, CDCl3)
δ155.0. FAB-HRMS: Calcd. for C48H58N6O8PSi+ [M+H]+;
905.3818. Found; 905.3826.
The same procedure as the synthesis of (Rp)-15 was ap-
plied for compound 13 (1.05 g, 1.47 mmol) and (4S, 5R)-14
(2.94 mmol). The crude product was purified by silica gel
column chromatography (NH-silica gel, toluene-AcOEt (8:2,
v/v) containing 0.1% triethylamine) to afford (Rp)-17
(0.62 g, 0.65 mmol, 44%).
1H NMR (400 MHz, CDCl3) δ 8.67 (s, 1H), 8.38-8.20 (br, 1H),
8.06 (s, 1H), 7.39-7.14 (m, 13H), 6.91-6.70 (m, 8H), 6.47 (t, J
= 6.4 Hz, 1H), 5.76 (d, J = 6.4 Hz, 1H), 5.22 (s, 2H), 5.09-5.03
(m, 1H), 4.29-4.26 (m, 1H), 3.89-3.74 (m, 13H), 3.62-3.54 (m,
1H), 3.41-3.33 (m, 2H), 3.20-3.11 (m, 1H), 2.99-2.92 (m, 1H),
2.71-2.65 (m, 1H), 1.68-1.59 (m, 2H), 1.26-1.16 (m, 1H),
1.03-0.94 (m, 1H). 13C{1H} NMR (75 MHz, CDCl3) δ 159.8,
158.9, 158.4, 158.4, 152.6, 150.9, 150.8, 149.4, 144.5, 141.4,
3
135.7, 135.6, 130.5, 130.2 (d, JPC = 3.7 Hz), 129.9, 129.9,
128.1, 127.7, 127.5, 126.8, 126.6, 122.4, 113.9, 113.6, 113.0,
86.4, 85.7, 84.8, 82.3 (d, 2JPC = 9.9 Hz), 73.3 (d, 2JPC = 11.1 Hz),
67.5, 67.5, 63.1, 55.2, 55.2, 55,1, 47.2 (d, 2JPC = 34.6 Hz), 39.1
Sp-dGtse monomer: (Sp)-18
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(d, JPC = 4.3 Hz), 28.1, 25.9 (d, JPC = 3.8 Hz). 31P{1H} NMR
(162 MHz, CDCl3) δ155.0. FAB-HRMS: Calcd. for
C52H53N6NaO10P+ [M+Na]+; 975.3453. Found; 975.3459.
The same procedure as the synthesis of (Rp)-18 was ap-
plied for O6-tse-5'-O-DMTr-2'-deoxyguanosine (0.67 g, 1.00
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