Molecules 2020, 25, 2161
8 of 12
)D20 32.50 (c 0.2, H O); H-NMR (D O):
1
δ
8.72 and 7.93
4
d
was obtained as an oil (11.16 mg, 31%): (
α
2
2
(
4H, Ph), 7.70 and 7.38 (2d, each 2H, Ph), 5.20 (s, 1H, H-1), 5.06 (dd, 1H, H-3, J3,4 1.2), 4.99 (dd, 1H,
0
0
0
3.8), 3.41 (s,
4,5
H-5, J4,5 3.8; J5,5 14), 4.94 (d, 1H, H-2, J2,3 6.0), 4.76 (m, 1H, H-4), 4.65 (dd, 1H, H-5 , J
3
H, -OCH ), 2.92 (s, 3H, PhCH -amine), 2.42 (s, 3H, PhCH ), 1.53 and 1.42 (2s, each 3H, C(CH ) );
3 3 3 3 2
1
3
C-NMR (H O) δ 146.19–142.55; 130.71 and 125.71 (Ph-amine), 129.63 and 125.60 (C, Ph), 114.06 (C,
2
C(CH ) ), 110.78 (C-1), 83.68 (C-4), 84.32 (C-2), 81.66 (C-3), 59.80 (C-5), 56.49 (C, OCH ), 25.58 and 24.06
3
2
3
+
(
C, C(CH ) ), 20.70 (C, PhCH ); MALDI TOF- MS (CCA): m/z 280.2 ((M-OTs) ).
3 2 3
N-((methyl 5-deoxy-2,3-O-isopropylidene-
tosylate (4e).
Procedure 1. Compound
β
-D-ribofuranoside)-5-yl)-4-(N,N-dimethylamino)-pyridinium
3
(30 mg; 0.084 mmol) and 4-(N,N-dimethylamino)pyridine (5.2 mg) was
◦
melted and conditioned at 100 C for 48 h. Compound 4e was obtained as a light oil (14.5 mg; 70%).
Procedure 2. Compound
3
(36 mg; 0.1 mmol) and 4-(N,N-dimethylamino)pyridine (6.15 mg) were
◦
dissolved in CH CN (1.5 mL). The solution was conditioned at 70 C for a month. Compound 4e was
3
20
1
obtained as an oil (9.1 mg; 37%); (
α
)D 21.50 (c 0.2, H O); H-NMR (D O):
δ
7.95 and 6.87 (4H, Ph),
2
2
7
4
6
.67 and 7.33 (2d, each 2H, Ph), 5.14 (s, 1H, H-1), 4.93 (dd, 1H, H-3, J3 0.8), 4.87 (d, 1H, H-2, J2,3 5.6),
,4
0
0
.63 (dd, 1H, H-4, J4,5 4.6), 4.40 (dd, 1H, H-5, J5,5 14.8), 4.12 (m, 1H, H-5 ), 3.44 (s, 3H, -OCH ), 3.19 (s,
3
13
H, N(CH ) ), 2.38 (s, 3H, PhCH ), 1.52 and 1.40 (2s, each 3H, C(CH ) ); C-NMR (H O)
δ 141.66 and
3
2
3
3 2
2
1
07.89; (Ph-amine), 129.61 and 125.58 (C, Ph), 113.83 (C, C(CH ) ), 110.47 (C-1), 85.10 (C-4), 84.48 (C-2),
3
2
8
1.35 (C-3), 59.44 (C-5), 56.30 (C, OCH ), 39,64 (C, N(CH ) ), 25.54 and 24.00 (C, C(CH ) ), 20.70 (C,
3
3 2
3 2
+
PhCH ); MALDI TOF- MS (CCA): m/z 309.4 ((M-OTs) ).
3
N-((methyl 5-deoxy-2,3-O-isopropylidene-β-D-ribofuranoside)-5-yl)isoquinolinium tosylate (4f). Compound
3
(30 mg; 0.084 mmol) was added to isoquinoline (0.23 g). After 9 days, compound 4f was obtained as a
20
1
light oil (29.9 mg, 72%); (α)D 23.00 (c 0.2, H O); H-NMR (D O): δ 9.65–8.04 (7H, Ph), 7.63 and 7.28 (2d,
2 2
each 2H, Ph), 5.16 (s, 1H, H-1), 5.08 (m, 2H, H-3, H-5), 4.93 (d, 1H, H-2, J 5.6), 4.89 (dd, 1H, H-4, J3,4 3.6,
2
,3
0
0
J4,5 10.4), 4.77 (dd, 1H, H-5 , J
13.4), 3.45 (s, 3H, -OCH ), 2.35 (s, 3H, PhCH ), 1.52 and 1.42 (2s, each 3H,
C(CH ) ); C-NMR (H O) δ 149.96–130.43 and 127.78–126.93 (Ph-amine), 129.57–125.53 (C, Ph), 113.98 (C,
5,5
3
3
13
3
2
2
C(CH ) ), 110.79 (C-1), 85.03 (C-4), 84.43 (C-2), 81.50 (C-3), 63.18 (C-5), 56.47 (C, OCH ), 25.52 and 24.01 (C,
3
2
3
+
C(CH ) ), 20.65 (C, PhCH ); MALDI TOF- MS (CCA): m/z 316.1 ((M-OTs) ).
3
2
3
3
.3. Procedure for 6a–6f
N-((methyl 5-deoxy-2,3-O-isopropylidene-
β
-D-ribofuranoside)-5-yl)trimethylammonium mesylate (6a).
Compound 5 (44 mg, 0.14 mmol) was dissolved in a 33% ethanolic solution of trimethylamine (0.12 mL)
and conditioned for 120h. After crystallization from 2-butanon, 6a was obtained (38.6 mg, 72%);
◦
20
1
mp. 153-155 C; (
α
)D -24.00 (c 0.2, H O); H-NMR (D O):
δ
5.24 (s, 1H, H-1), 4.91 (dd, 1H, H-3, J
2
2
3.4
0
1
.6), 4.83 (d, 1H, H-2, J 6.0), 4.79 (m, 1H, H-4), 3.71 (dd, 1H, H-5, J4,5 2.4, J5,5 14.0), 3.57 (dd, 1H,
H-5 , J4 9.6), 3.49 (s, 3H, -OCH ), 3.28 (s, 9H, N(CH ) ), 2.83 (s, 3H, -CH ), 1.57 and 1.41 (2s, each
H, C(CH ) ); C-NMR (H O) δ 114.08 (C, C(CH ) ), 110.44 (C-1), 83.88 (C-2), 83.10 (C-3), 81.17 (C-4),
3 2 2 3 2
2,3
0
0
,5
3
3 3
3
13
3
6
8.92 (C-5), 56.34 (C, OCH ), 54.29 (C, N(CH ) ), 38.72 (CH -), 25.65 and 24.06 (C, C(CH ) ); MALDI
3
3 3
3
3 2
+
TOF- MS (CCA): m/z 246.2 ((M-OMs) ).
N-((methyl 5-deoxy-2,3-O-isopropylidene-β-D-ribofuranoside)-5-yl)triethylammonium mesylate (6b).
Compound
compound 6b was obtained as an oil (10.8 mg, 19%); (
H, H-1), 4.90 (dd, 1H, H-3, J2 6.0; J3.4 2.0), 4.81 (d, 1H, H-2, J2,3 5.6), 4.61 (m, 1H, H-4), 3.48 (m, 2H,
5 (40 mg, 0.14 mmol) was dissolved in dry triethylamine (0.12 mL). After 30 days,
20
1
α
)D -0.8 (c 0.2, H O); H-NMR (D O): δ 5.21 (s,
2 2
1
,3
0
H-5 and H-5 ), 3.48 (s, 3H, -OCH ), 3.48-3.20 and 1.30 (15H, NEt ), 2.83 (s, 3H, -CH ), 1.55 and 1.40 (2s,
each 3H, C(CH ) ); MALDI TOF- MS (CCA): m/z 288.2 ((M-OMs) ).
3
3
3
+
3
2
N-((methyl 5-deoxy-2,3-O-isopropylidene-
Compound
compound 6c was obtained as an oil (33.8 mg; 66%); (
.91–8.16 (t,t,d, 5H, Ph), 5.19 (s, 1H, H-1), 5.07 (dd, 1H, H-3, J3,4 1.2), 5.01 (dd, 1H, H-5, J
β
-D-ribofuranoside)-5-yl)pyridinium mesylate
(6c).
5
(40 mg, 0.04 mmol) was dissolved in dry pyridine (0.26 mL).After 14 days,
20
1
α
)D 16.40 (c 0.2, H O); H-NMR (D O): δ
2 2
0
8
13.2), 4.94
5,5
0 0
d, 1H, H-2, J2,3 6.0), 4.76 (m, 1H, H-4, J4,5 5.0; J4,5 10.4), 4.67 (m, 1H, H-5 ), 3.46 (s, 3H, -OCH ), 2.83 (s,
3
(