Full Papers
Jgem =11.8 Hz, J5’b,OH =5.2 Hz, J5’b,4’ =3.9 Hz, H-5’b), 3.93 (td, 1H,
furyl), 127.1 (CH-6), 144.7 (CH-5-furyl), 144.9 (C-2-furyl), 150.1 (C-4),
152.7 (C-7a), 159.9 ppm (C-2); IR (ATR): n˜ =3152, 3119, 1598, 1568,
1552, 1511, 1460, 1407, 1366, 1255, 1243, 1199, 1162, 1066, 965,
J4’,5’a =J4’,5’b =3.9 Hz, J4’,3’ =3.0 Hz, H-4’), 4.11 (td, 1H, J3’,2’ =J3’,OH
=
4
5
.9 Hz, J3’,4’ =3.0 Hz, H-3’), 4.46 (td, 1H, J2’,1’ =J2’,OH =6.5 Hz, J2’,3’
.1 Hz, H-2’), 5.14 (dd, 1H, JOH,5’a =6.0 Hz, JOH,5’b =5.2 Hz, OH-5’), 5.19
=
À1
+
871, 768, 723, 641, 604 cm ; MS (ESI) m/z (%): 332 (90) [M+H] ,
+
+
(
(
d, 1H, JOH,3’ =4.7 Hz, OH-3’), 5.35 (d, 1H, JOH,2’ =6.5 Hz, OH-2’), 6.20
d, 1H, J1’,2’ =6.5 Hz, H-1’), 6.77 (dd, 1H, J4,3 =3.5 Hz, J4,5 =1.8 Hz, H-
354 (100) [M+Na] ; HRMS (ESI) for C H O N Na [M+Na] calcd:
16 17 5 3
354.10604, found: 354.10575; Anal. calcd for C H O N : C 58.00, H
16
17
5
3
4
-furyl), 6.99 (bd, 1H, J5,6 =3.8 Hz, H-5), 7.43 (dd, 1H, J3,4 =3.5 Hz,
5.17, N 12.68, found: C 57.94, H 5.08, N 12.54.
J3,5 =0.9 Hz, H-3-furyl), 7.81 (d, 1H, J6,5 =3.8 Hz, H-6), 8.04 ppm (dd,
13
2-Methyl-4-(thien-3-yl)-7-(b-d-ribofuranosyl)-7H-pyrrolo[2,3-d]-
pyrimidine (6d). Compound 16 (150 mg, 0.5 mmol) was reacted
with 2-thienylboronic acid (96 mg, 0.75 mmol) for 10 min according
to general procedure B to give 6d as a beige solid (158 mg, 91%)
1
H, J5,4 =1.8 Hz, J5,3 =0.8 Hz, H-5-furyl);
C NMR (125.7 MHz,
[
D ]DMSO): d=25.8 (CH ), 61.9 (CH -5’), 71.0 (CH-3’), 73.9 (CH-2’),
6
3
2
8
5.5 (CH-4’), 86.7 (C-1’), 101.2 (CH-5), 110.7 (C-4a), 112.8 (CH-4-
furyl), 113.2 (CH-3-furyl), 127.6 (CH-6), 146.3 (CH-5-furyl), 146.6 (C-
that was recrystallized from H O/MeOH 4:1 to provide a beige
2
4
3
), 152.7 (C-2-furyl), 153.2 (C-7a), 160.0 ppm (C-2); IR (ATR): n˜ =
2
D
0
1
À1
solid: mp: 213–2168C; [a]
(500 MHz, [D
1
=À59.5 (c=0.237, DMSO); H NMR
143, 3127, 2927, 2910, 1602, 1568, 1517, 1254 cm ; MS (ESI) m/z
+
+
6
]DMSO): d=2.69 (s, 3H, CH
3
), 3.56 (ddd, 1H, Jgem
=
=
=
(
%): 332 (100) [M+H] ; HRMS (ESI) for C H O N [M+H] calcd:
16 18 5 3
1.9 Hz, J5’a,OH =6.0 Hz, J5’a,4’ =4.0 Hz, H-5’a), 3.64 (ddd, 1H, Jgem
1.8 Hz, J5’b,OH =5.2 Hz, J5’b,4’ =4.0 Hz, H-5’b), 3.93 (td, 1H, J4’,5’a
3
5
32.12410, found: 332.12418; Anal. calcd for C H O N ·0.4H O: C
16 17 5 3 2
6.77, H 5.30, N 12.41, found: C 57.08, H 5.18, N 12.11.
1
J4’,5’b =4.0 Hz, J4’,3’ =3.1 Hz, H-4’), 4.12 (td, 1H, J3’,2’ =J3’,OH =4.9 Hz,
J3’,4’ =3.1 Hz, H-3’), 4.47 (td, 1H, J2’,1’ =J2’,OH =6.5 Hz, J2’,3’ =5.2 Hz, H-
2’), 5.14 (dd, 1H, JOH,5’a =6.0 Hz, JOH,5’b =5.2 Hz, OH-5’), 5.19 (d, 1H,
JOH,3’ =4.7 Hz, OH-3’), 5.35 (d, 1H, JOH,2’ =6.5 Hz, OH-2’), 6.22 (d, 1H,
2
-Methyl-4-(thien-2-yl)-7-(b-d-ribofuranosyl)-7H-pyrrolo[2,3-d]-
pyrimidine (6b). Compound 16 (150 mg, 0.5 mmol) was reacted
with 2-thienylboronic acid (96 mg, 0.75 mmol) for 15 min according
to general procedure B to give 6b as a beige solid (169 mg, 97%)
J1’,2’ =6.6 Hz, H-1’), 7.05 (d, 1H, J5,6 =3.8 Hz, H-5), 7.73 (dd, 1H, J5,4
=
that was recrystallized from H O/MeOH 4:1 to provide a beige
5.1 Hz, J5,2 =2.9 Hz, H-5-thienyl), 7.82 (d, 1H, J6,5 =3.8 Hz, H-6), 7.93
(dd, 1H, J4,5 =5.1 Hz, J4,2 =1.3 Hz, H-4-thienyl), 8.49 ppm (dd, 1H,
2
20
1
solid: mp: 204–2068C; [a] =À64.5 (c=0.244, DMSO); H NMR
D
13
(
1
1
500 MHz, [D ]DMSO): d=2.66 (s, 3H, CH ), 3.56 (ddd, 1H, J
gem
1.9 Hz, J5’a,OH =5.8 Hz, J5’a,4’ =3.8 Hz, H-5’a), 3.64 (ddd, 1H, Jgem
1.9 Hz, J5’b,OH =5.3 Hz, J5’b,4’ =4.1 Hz, H-5’b), 3.93 (btd, 1H, J4’,5’a
=
=
=
J2,5 =2.9 Hz, J2,4 =1.3 Hz, H-2-thienyl);
C NMR (125.7 MHz,
6
3
[D ]DMSO): d=25.9 (CH ), 61.9 (CH -5’), 71.0 (CH-3’), 73.9 (CH-2’),
6
3
2
85.4 (CH-4’), 86.7 (C-1’), 101.0 (CH-5), 112.5 (C-4a), 127.2 (CH-5-
thienyl), 127.4 (CH-6), 127.7 (CH-4-thienyl), 128.5 (CH-2-thienyl),
140.2 (C-3-thienyl), 151.6 (C-4), 153.1 (C-7a), 159.8 ppm (C-2); IR
(ATR): n˜ =3426, 3115, 3101, 2924, 1572, 1566, 1518, 1464, 1405,
1367, 1348, 1289, 1241, 1176, 1116, 1079, 1052, 1044, 969, 898, 842,
J4’,5’b =4.0 Hz, J4’,3’ =3.0 Hz, H-4’), 4.12 (td, 1H, J3’,2’ =J3’,OH =4.9 Hz,
J3’,4’ =3.0 Hz, H-3’), 4.47 (td, 1H, J2’,1’ =J2’,OH =6.4 Hz, J2’,3’ =5.3 Hz, H-
2
4
6
5
1
1
’), 5.14 (bt, 1H, JOH,5’a =JOH,5’b =5.5 Hz, OH-5’), 5.20 (d, 1H, JOH,3’
.7 Hz, OH-3’), 5.36 (d, 1H, JOH,2’ =6.4 Hz, OH-2’), 6.21 (d, 1H, J1’,2’
.5 Hz, H-1’), 7.10 (d, 1H, J5,6 =3.8 Hz, H-5), 7.29 (dd, 1H, J4,5
.1 Hz, J4,3 =3.8 Hz, H-4-thienyl), 7.83 (dd, 1H, J5,4 =5.1 Hz, J5,3
=
=
=
=
À1
+
770, 720, 688, 609 cm ; MS (ESI) m/z (%): 348 (100) [M+H] , 370
+
+
(80) [M+Na] ; HRMS (ESI) for C H O N S [M+H]
calcd:
16
18
4
3
.1 Hz, H-5-thienyl), 7.84 (d, 1H, J6,5 =3.9 Hz, H-6), 8.14 ppm (dd,
348.10125, found: 348.10126; Anal. calcd for C H O N S·0.1H O: C
16
17
4
3
2
13
H, J3,4 =3.8 Hz, J3,5 =1.1 Hz, H-3-thienyl); C NMR (125.7 MHz,
55.03, H 4.96, N 12.03, found: C 55.56, H 5.04, N 11.53.
[
D ]DMSO): d=25.7 (CH ), 61.9 (CH -5’), 70.9 (CH-3’), 74.0 (CH-2’),
4.5 (CH-4’), 86.7 (C-1’), 100.8 (CH-5), 110.9 (C-4a), 127.7 (CH-6),
29.1 (CH-4-thienyl), 129.6 (CH-3-thienyl), 130.7 (CH-5-thienyl),
6
3
2
2
-Methyl-4-phenyl-7-(b-d-ribofuranosyl)-7H-pyrrolo[2,3-d]pyrimi-
8
1
1
dine (6e). Compound 16 (150 mg, 0.5 mmol) was reacted with
phenylboronic acid (91 mg, 0.75 mmol) for 10 min according to
general procedure B to give 6e as a colorless oil (126 mg, 74%)
42.8 (C-2-thienyl), 150.2 (C-4), 153.2 (C-7a), 159.7 ppm (C-2); IR
À1
(
ATR): n˜ =3139, 3114, 2922, 2830, 1565, 1517, 1271 cm ; MS (ESI)
+
+
that was recrystallized from H O/MeOH 4:1 to provide a white
2
m/z (%): 348 (85) [M+H] , 370 (100) [M+Na] ; HRMS (ESI) for
C H O N S [M+H] calcd: 348.10125, found: 348.10064; Anal.
calcd for C H O N S·0.15H O: C 54.89, H 4.98, N 12.00, found: C
5
2
D
0
1
+
solid: mp: 92–958C; [a]
500 MHz, [D ]DMSO): d=2.73 (s, 3H, CH ), 3.56 (ddd, 1H, J
gem
=À51.1 (c=0.217, DMSO); H NMR
1
6
18
4
3
(
=
=
=
6
3
1
6
17
4
3
2
11.9 Hz, J5’a,OH =5.9 Hz, J5’a,4’ =3.9 Hz, H-5’a), 3.64 (ddd, 1H, Jgem
5.26, H 4.91, N 11.61.
11.9 Hz, J5’b,OH =5.1 Hz, J5’b,4’ =4.0 Hz, H-5’b), 3.94 (td, 1H, J4’,5’a
2
-Methyl-4-(furan-3-yl)-7-(b-d-ribofuranosyl)-7H-pyrrolo[2,3-d]-
J4’,5’b =4.0 Hz, J4’,3’ =3.0 Hz, H-4’), 4.13 (td, 1H, J3’,2’ =J3’,OH =4.9 Hz,
J3’,4’ =3.0 Hz, H-3’), 4.49 (td, 1H, J2’,1’ =J2’,OH =6.5 Hz, J2’,3’ =5.1 Hz, H-
pyrimidine (6c). Compound 16 (150 mg, 0.5 mmol) was reacted
with 3-furylboronic acid (84 mg, 0.75 mmol) for 15 min according
to general procedure B to give 6c as a light-yellow oil (162 mg,
2’), 5.13 (t, 1H, JOH,5’a =JOH,5’b =5.5 Hz, OH-5’), 5.20 (d, 1H, JOH,3’
4.7 Hz, OH-3’), 5.36 (d, 1H, JOH,2’ =6.5 Hz, OH-2’), 6.24 (d, 1H, J1’,2’
=
=
9
8%) that was recrystallized from H O/MeOH 4:1 to provide beige
6.5 Hz, H-1’), 6.92 (d, 1H, J5,6 =3.8 Hz, H-5), 7.53–7.61 (m, 3H, H-
2
20
1
needles: mp: 191–1938C; [a] =À55.9 (c=0.227, DMSO); H NMR
p,m-Ph), 7.83 (d, 1H, J =3.8 Hz, H-6), 8.14 ppm (m, 2H, H-o-Ph);
D
6,5
13
(
500 MHz, [D ]DMSO): d=2.67 (s, 3H, CH ), 3.56 (ddd, 1H, J
=
=
=
C NMR (125.7 MHz, [D ]DMSO): d=25.9 (CH ), 61.9 (CH -5’), 71.0
6
3
gem
6
3
2
11.9 Hz, J5’a,OH =6.0 Hz, J5’a,4’ =4.0 Hz, H-5’a), 3.64 (ddd, 1H, Jgem
(CH-3’), 74.0 (CH-2’), 85.5 (CH-4’), 86.7 (CH-1’), 100.9 (CH-5), 113.4
(C-4a), 127.5 (CH-6), 128.8 (CH-o-Ph), 129.1 (CH-m-Ph), 130.3 (CH-p-
Ph), 137.9 (C-i-Ph), 153.1 (C-7a), 156.3 (C-4), 160.0 ppm (C-2); IR
(ATR): n˜ =3430, 3070, 2928, 1606, 1587, 1496, 1466, 1404, 1361,
1287, 1270, 1237, 1125, 1114, 1087, 1078, 1044, 1030, 1002, 898,
11.9 Hz, J5’b,OH =5.2 Hz, J5’b,4’ =4.0 Hz, H-5’b), 3.93 (td, 1H, J4’,5’a
J4’,5’b =3.9 Hz, J4’,3’ =3.0 Hz, H-4’), 4.12 (td, 1H, J3’,2’ =J3’,OH =4.9 Hz,
J3’,4’ =3.0 Hz, H-3’), 4.47 (td, 1H, J2’,1’ =J2’,OH =6.5 Hz, J2’,3’ =5.1 Hz, H-
2
JOH,3’ =4.9 Hz, OH-3’), 5.34 (d, 1H, JOH,2’ =6.5 Hz, OH-2’), 6.20 (d, 1H,
J1’,2’ =6.5 Hz, H-1’), 7.01 (bd, 1H, J5,6 =3.9 Hz, H-5), 7.23 (dd, 1H,
J4,5 =1.9 Hz, J4,2 =0.8 Hz, H-4-furyl), 7.79 (d, 1H, J6,5 =3.9 Hz, H-6),
’), 5.15 (dd, 1H, JOH,5’a =6.0 Hz, JOH,5’b =5.1 Hz, OH-5’), 5.19 (d, 1H,
À1
+
883, 694, 668 cm ; MS (ESI) m/z (%): 342 (100) [M+H] , 364 (25)
+
+
[M+Na] ; HRMS (ESI) for C H O N [M+H] calcd: 342.14483,
18
20
4
3
found: 342.14487; Anal. calcd for C H O N ·1.8H O: C 57.84, H
18
19
4
3
2
7
1
2
.88 (bt, 1H, J5,4 =J5,2 =1.7 Hz, H-5-furyl), 8.68 ppm (dd, 1H, J
=
6.09, N 11.24, found: C 58.09, H 6.03, N 10.94.
2,5
13
.5 Hz, J2,4 =0.8 Hz, H-2-furyl); C NMR (125.7 MHz, [D ]DMSO): d=
6
2
-Methyl-4-(benzofuran-2-yl)-7-(b-d-ribofuranosyl)-7H-pyrrolo-
5.9 (CH ), 61.9 (CH -5’), 70.9 (CH-3’), 73.9 (CH-2’), 85.4 (CH-4’), 86.7
3
2
[2,3-d]pyrimidine (6 f). Compound 16 (150 mg, 0.5 mmol) was re-
(
C-1’), 100.7 (CH-5), 109.6 (CH-4-furyl), 112.4 (C-4a), 125.3 (CH-3-
acted with 2-benzofurylboronic acid (121 mg, 0.75 mmol) for
&
ChemMedChem 0000, 00, 0 – 0
8
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