Chem. Pap.
0
0
0 0
(m, 1H, 2 -H), 4.34–4.30 (m, 1H, 3 -H), 4.09–4.05 (m, 1H,
H ? 5 -OH), 5.79 (dd, J = 8.6, 3.9 Hz, 1H, 3 -OH), 5.45
0
0
0
0
13
(
dd, J = 7.4, 4.9 Hz, 1H, 2 -H), 4.36–4.32 (m, 1H, 3 -H),
4 -H), 3.27–3.18 (m, 2H, 5 -H). C NMR (126 MHz,
DMSO) d 156.54 (6-C), 153.06 (2-C), 149.76 (4-C), 144.09
(Ph), 140.07 (8-C), 128.71 (Ph), 128.31 (Ph), 127.47
0 0
13
4
3
.07–4.04 (m, 1H, 4 -H), 3.67–3.62 (m, 1H, 5 -H),
0
.58–3.51 (m, 1H, 5 -H), 2.26 (s, 3H, –CH ). C NMR
3
0 0 0
0 0
73.42 (Ph C-), 70.73 (3 -C), 64.36 (5 -C).
3
(
(
(
(
126 MHz, DMSO) d 156.53 (6-C), 152.36 (2-C), 148.28
(Ph),119.66 (5-C), 88.43 (4 -C), 86.51 (1 -C), 83.33 (2 -C),
4-C), 145.42 (Ph-C), 140.28 (8-C), 131.68 (Ph-C), 129.79
0
Ph-C), 127.12 (Ph-C), 119.97 (5-C), 87.79 (4 -C), 85.33
0
0
0
0
0
0
1 -C), 79.37 (2 -C), 70.27 (3 -C), 62.03 (5 -C), 21.54 (–
Synthesis of 3 -O-tosyl-5 -O-
triphenylmethyladenosine (19)
CH3).
0
0
Synthesis of 2 -deoxyadenosine (17)
5 -O-triphenylmethyladenosine 18 (2.55 g, 5 mmol) and
anhydrous DMF (30 mL) were placed in a 100 mL round-
bottom flask. Triethylamine (10 mL) and p-toluenesulfonyl
chloride (1.91 g, 10 mmol) were added to the reaction
mixture while stirring. The reaction mixture was stirred at
30 °C for 24 h, which was sampled and showed no or very
0
Under nitrogen atmosphere, 2 -O-p-toluenesulfony-
ladenosine 16 (2.11 g, 5 mmol) and anhydrous tetrahy-
drofuran (THF, 35 mL) were placed in a 100 mL round-
bottom flask. Lithium aluminum hydride in anhydrous THF
0
(
LiAlH /THF, 1 M, 25 mL) was slowly dropped to the
4
low amounts of 5 -O-triphenylmethyladenosine 18 being
solution and the resulting mixture was stirred at 0–5 °C for
detected by TLC, and it showed two new points on the
thin-layer. Then, ethyl acetate (50 mL) was added to the
reaction mixture to dissolve the crude product and the
solution was washed with saturated salt water for three
times. The organic layer was dried with anhydrous sodium
sulfate, concentrated in vacuo to afford the crude product
19 as a yellow liquid. The crude product was purified by
flash chromatography on silica gel using dichloromethane/
methanol (40:1) as eluents to afford pure 19 (2.35 g,
4
h and was then continued to stir at room temperature for
6
h. After reaction completion, the mixture was carefully
quenched with 10 mL of methanol, concentrated in vacuo,
and recrystallization from ethanol to afford pure 17
(
(
1.06 g, 84.6%) as a white powder with the purity of 98.3%
1
HPLC). H NMR (400 MHz, DMSO-d ) d 8.34 (s, 1H,
6
8
-H), 8.13 (s, 1H, 2-H), 7.32 (s, 2H, –NH ), 6.35 (dd,
2
0
J = 7.9, 6.1 Hz, 1H, 1 -H), 5.31 (dd, J = 4.0, 1.3 Hz, 1H,
0
0
3
-OH), 5.25 (dd, J = 6.6, 4.8 Hz, 1H, 5 -OH), 4.43–4.39
0
70.7%) as a white powder with the purity of 97.5%
1
0
(
m, 1H, 3 -H), 3.90–3.87 (m, 1H, 4 -H), 3.65–3.60 (m, 1H,
(HPLC). H NMR (400 MHz, DMSO-d ) d 8.13 (s, 1H,
6
0
0
0
5
2
1
1
6
-H), 3.55–3.49 (m, 1H, 5 -H), 2.77–2.70 (m, 1H, 2 -H),
0
8-H), 7.86 (s, 1H, 2-H), 7.47 (d, J = 8.4 Hz, 2H, Ts-H),
13
.28–2.23 (m, 1H, 2 -H). C NMR (126 MHz, DMSO) d
56.56 (6-C), 152.84 (2-C), 149.34 (4-C), 140.03 (8-C),
7.39–7.35 (m, 7H, Tr-H ? –NH ), 7.32–7.25 (m, 10H, Tr-
2
H), 7.06 (d, J = 8.1 Hz, 2H, Ts-H), 6.11 (d, J = 6.0 Hz,
0 0
0
0
0
19.72 (5-C), 88.46 (4 -C), 84.42 (1 -C), 71.45 (3 -C),
0
1H, 1 -H), 6.06 (d, J = 5.9 Hz, 1H, 2 -OH), 5.75 (d,
0 0
J = 6.2 Hz, 1H, 2 -H), 4.55–4.51 (m, 1H, 3 -H), 4.15–4.11
0
2.37 (5 -C), 39.44 (2 -C).
0
0
(
m, 1H, 4 -H), 3.33 (dd, J = 10.4, 4.3 Hz, 1H, 5 -H), 3.17
0
0
13
(dd, J = 10.5, 5.0 Hz, 1H, 5 -H), 2.28 (s, 3H, –CH ). C
Synthesis of 5 -O-triphenylmethyladenosine (18)
3
NMR (101 MHz, DMSO) d 156.36 (6-C), 152.66 (2-C),
148.90 (4-C), 145.48 (Ph), 143.93 (Ph), 140.36 (8-C),
132.11 (Ph), 129.89 (Ph), 128.68 (Ph), 128.35 (Ph), 127.54
In a 100 mL round-bottom flask, adenosine 2 (1.34 g,
mmol) and anhydrous N,N-dimethylformamide (30 mL)
5
0
0
was placed. Triphenylmethyl chloride (4.20 g, 15 mmol)
and triethylamine (10 mL) were added to the reaction
mixture while upon stirring at 45 °C for 24 h. Ethyl acetate
(Ph), 127.36 (Ph), 119.64 (5-C), 86.62 (4 -C), 85.32 (1 -C),
0
0
0
84.19 (Ph C-), 79.11 (2 -C), 69.30 (3 -C), 63.35 (5 -C),
3
21.55 (–CH3).
(
50 mL) was added to the reaction mixture to dissolve the
0
0
crude product and washed with saturated salt water. The
organic layer was dried with anhydrous sodium sulfate and
concentrated in vacuo to afford the crude product 18 as an
orange liquid. The crude product was purified by flash
chromatography on silica gel using dichloromethane/
methanol (30:1) as eluents to afford pure 18 (2.16 g,
Synthesis of 5 -O-triphenylmethyl-3 -deoxyadenosine
(20)
0
0
3 -O-tosyl-5 -O-triphenylmethyladenosine 19 (3.32 g,
5 mmol) and THF (30 mL) were placed in a 100 mL
round-bottom flask. Lithium aluminum hydride in anhy-
7
5.0%) as a light yellow solid with the purity of 97.9%
1
drous THF (LiAlH /THF, 1 M, 25 mL) was slowly drop-
4
(
HPLC). H NMR (400 MHz, DMSO-d ) d 8.26 (s, 1H,
ped to the solution and the resulting mixture was stirred at
0–5 °C for 4 h. After reaction completion, the reaction
mixture was kept standing until the temperature reached
room temperature. Then, the mixture was carefully
6
2
-H), 8.10 (s, 1H, 8-H), 7.38–7.26 (m, 17H, Ph-H ? –
0
NH ), 5.93 (d, J = 4.5 Hz, 1H, 1 -H), 5.56 (d, J = 5.7 Hz,
2
0
0
1
H, 2 -OH), 5.23 (d, J = 5.9 Hz, 1H, 3 -OH), 4.72–4.68
123