European Journal of Organic Chemistry
10.1002/ejoc.202000650
FULL PAPER
(
m, 3H, H-5,H-6a, H-6b), -0.06 (s, 9H, TMS).13C NMR (101 MHz, CDCl3)
85.5 (C-1), 77.8 (C-5), 77.3 (OBn), 75.5 (C-3), 75.1 (OBn), 74.0 (OBn),
73.5 (C-4, C-2), 68.2 (C-6), 0.3 (TMS). HRMS (ESI+): m/z calcd. for
C34H39BrN2O7Si (M+H+2) 697.1788, found 697.1749.
δ 162.7 (C-10), 150.50 (C-8), 140.1 (C-12), 138.6, 137.8, 137.7(quaternary
aromatic), 128.5, 128.5, 128.3, 127.9, 127.9, 127.8, 127.7,
+
127.6(aromatic),104.0 (C-11), 83.3 (C-1), 83.2 (C-5), 76.0 (C-3),
7
(
4.9(OBn), 73.6 (C-4), 73.6 (OBn), 72.9 (OBn), 71.1 (C-2), 68.2 (C-6), 0.3
1
-{3',4',6'-Tri-O-(benzyl)-2-O-trimethylsilyl-β-D-glucopyranosyl}-4-
TMS). (ESI+): m/z calcd for C34H41N2O7Si (M+H)+ 617.2683, found
amino-2(lH,3H)-pyrimidinone (7g). 89 mg, 62%, gummy solid; 1H NMR
617.2669.
(400 MHz, CDCl3) δ 7.67 (d, J = 7.3 Hz, 0.15H), 7.41 – 7.26 (m, 16H, H-
12, aromatic), 7.17 – 7.13 (m, 2H, aromatic), 6.17 (d, J = 2.5 Hz, 0.13H,
1
-{3',4',6'-Tri-O-(benzyl)-2-O-trimethylsilyl-β-D-galactopyranosyl}-5-
H-1(α-nucleoside)), 5.95 (d, J = 6.6 Hz, 1H, H-1), 5.87 (s, 1H, H-11), 4.91
(s, 2H, OBn), 4.80 (d, J = 10.8 Hz, 1H, OBn), 4.61 – 4.49 (m, 4H, OBn),
3.80 – 3.59 (m, 7H, H-2, H-3, H-4, H-5, H-6a, H-6b), 0.00 (s, 9H, TMS(β-
nucleoside)), -0.01 (s, 1.41H, TMS(α-nucleoside).13C NMR (101 MHz,
CDCl3) δ 165.2 (C-10), 156.0 (C-8), 140.8 (C-12), 138.6, 138.0, 137.9
(quaternary aromatic), 128.5, 128.4, 128.3, 127.91, 127.8, 127.8, 127.8,
127.4, 127.2 (aromatic), 95.9 (C-11), 86.1 (C-1), 77.7 (C-5), 77.6 (OBn),
77.3 (C-3), 75.6 (OBn), 75.0 (OBn), 74.6 (C-4), 73.5 (C-2), 68.6 (C-6), 0.3
(TMS). HRMS (ESI+): m/z calcd. for C34H42N3O6Si (M+H)+ 616.2843,
found 616.2833.
chloro-2,4(1H,3H)-pyrimidinedione (7c).99 mg, 66%, gummy solid; 1
H
NMR (400 MHz, CDCl3) δ 9.11 (d, J = 11.1 Hz, 1H, H-9), 7.47 (s, 1H, H-
2), 7.30 – 7.19 (m, 15H, aromatic), 5.52 (d, J = 8.7 Hz, 1H, H-1), 4.83 (d,
J = 11.4 Hz, 1H, OBn), 4.62 (s, 1H, OBn), 4.50 – 4.33 (m, 3H, OBn), 3.96
t, J = 8.9 Hz, 1H, H-2), 3.85 (s, 1H, H-4), 3.71 (t, J = 6.3 Hz, 1H, H-3),
.51 – 3.46 (m, 3H, H-5, H-6a, H-6b), -0.06 (s, 9H, TMS).13C NMR (101
1
(
3
MHz, CDCl3) δ 158.5(C-10), 149.7 (C-8), 138.4, 137. 8, 137.6,(quaternary
aromatic), 137.0 (C-12), 128.5, 128.4, 128.0, 127.9, 127.9, 127.8, 127.7
(aromatic), 109.8(C-11), 83.7(C-1), 83.1(C-5), 76.3(C-3), 74.8(OBn), 73.6
(C-4), 73.5(OBn), 72.9(OBn), 71.1(C-2), 68.3(C-6), 0.3 (TMS). HRMS
(
ESI+): m/z calcd. for C34H43ClN3O7Si (M+NH4)+ 668.2559, found
1
-{3',4',6'-Tri-O-(benzyl)-2-O-trimethylsilyl-β-D-glucopyranosyl}-9-
668.2522.
purine-6-amine (7h).85 mg, 57%, gummy solid; 1H NMR (400 MHz,
CDCl3) δ 8.71 (s, 1H), 8.47 (s, 1H), 7.38 – 7.24 (m, 13H, aromatic), 7.15 –
7.11 (m, 2H, aromatic), 6.00 – 5.90 (m, 2H, H-1, NH), 5.00 – 4.78 (m, 3H,
OBn), 4.54 (d, J = 11.0 Hz, 1H, OBn), 4.46 (s, 2H, OBn), 4.30 (dd, J = 9.4,
4.9 Hz, 1H, H-5), 4.09 (t, J = 8.9 Hz, 1H, H-2), 3.76 (t, J = 8.9 Hz, 1H), 3.66
(dd, J = 10.9, 4.6 Hz, 1H), 3.61 – 3.55 (m, 1H), 3.50 (d, J = 9.5 Hz, 1H,
NH), 0.10 (s, 9H). 13C NMR (126 MHz, CDCl3) δ 160.4, 153.4, 151.7, 144.9,
137.6, 137.5, 137.2, 128. 8, 128.6, 128.6, 128.5, 128.4, 128.2, 128.1,
128.0, 128.0, 127.9, 127.7, 127.0, 111.6, 83.2 (C-1), 81.5 (C-5), 75.8
(OBn), 75.0 (C-3), 73.4 (OBn), 72.6 (OBn, C-2), 67.5 (C-6), -0.0. HRMS
1
2
-{3',4',6'-Tri-O-(benzyl)-2-O-trimethylsilyl-β-D-glucopyranosyl}-
,4(1H,3H)-pyrimidinedione (7d). 96 mg, 67%, gummy solid, 1H NMR
(400 MHz, CDCl3) δ 9.46 (s, 1H,H-9), 7.62 (d, J = 8.2 Hz, 0.17H, H-12(α-
nucleoside)), 7.39 – 7.26 (m, 17H, H-12(β-nucleoside), aromatic), 7.15-
7
5
.09 (m, 2H, aromatic), 6.10 (d, J = 2.7 Hz, 0.16H, H-1(α-nucleoside)),
.85 (d, J = 8.1 Hz, 1H, H-11(β-nucleoside)), 5.72 – 5.64 (m, 1.11H, H-1(β-
nucleoside), H-11(α-nucleoside)), 4.91 (q, J = 11.4 Hz, 2H, OBn), 4.78 (d,
J = 10.7 Hz, 1H, OBn), 4.67 (s, 0.19H), 4.60 – 4.49 (m, 4H, OBn,), 4.43 (s,
+
0
6
.38H), 4.36 (s, 0.19H), 3.80 – 3.67 (m, 7H,H-2, H-3, H-4, H-5, H-6a, H-
b)), 0.02 (s, 9H, TMS(β-nucleoside)), 0.00 (s, 1.52H, TMS(α-
(ESI+): m/z calcd. for C35H42N5O5Si (M+H) 640.3000, found 640.3012.
1
3
nucleoside)). C NMR (101 MHz, CDCl3) δ 162.9 (C-10), 150.7 (C-8),
1-{3',4',6'-Tri-O-(tert-butyldimethylsilyl)-2-O-trimethylsilyl-β-D-
1
1
8
7
39.8 (C-12), 138.4, 137.9, 137.8 (quaternary aromatic), 128.5, 128.5,
28.4, 127.9, 127.9, 127.8, 127.7, 127.5, 127.2 (aromatic), 103.3 (C-11),
5.7 (C-1), 77.7 (C-5), 77.5 (OBn), 75.6 (C-3), 75.1 (OBn), 74.0 (OBn),
glucopyranosyl)}-2,4(1H,3H)-pyrimidinedione (7i). 110 mg, 82%,
gummy solid; 1H NMR (400 MHz, CDCl3) δ 9.54 (s, 1H, H-9), 7.62 (d, J =
8.1 Hz, 1H, H-12), 5.97 (d, J = 2.6 Hz, 1H, H-1), 5.67 (d, J = 7.9 Hz, 1H,
3.5 (C-4, C-2), 68.4 (C-6), 0.3 (TMS). HRMS (ESI+): m/z calcd. for
H-9), 4.20 – 4.14 (m, 1H, H-5), 4.09 – 4.06 (m, 1H, H-2), 3.89 (dd, J = 10.8,
+
C34H41N2O7Si (M+H) 617.2683, found 617.2669.
3
1
.8 Hz, 1H, H-6a), 3.82 (d, J = 3.1 Hz, 1H, H-3), 3.74 (dd, J = 10.8, 7.0 Hz,
H, H-6b), 3.66 (d, J = 6.2 Hz, 1H, H-4), 0.92 (s, 7H, TBS), 0.91-0.87 (m,
1
-{3',4',6'-Tri-O-(benzyl)-2-O-trimethylsilyl-β-D-glucopyranosyl}-5-
20H, TBS), 0.17 – 0.05 (m, 18H, TBS), 0.02 (s, 9H, TMS). 13C NMR (101
MHz, CDCl3) δ 164.1 (C-10), 150.0 (C-8), 142.4 (C-12), 100.4 (C-11), 79.6
(C-5), 79.0 (C-1), 74.6 (C-3), 71.0 (C-4), 69.0 (C-2), 62.9 (C-6), 25.8, 25.7,
25.7, 18.2, 17.8 (TBS), -0.4 (TMS), -4.1, -4.5, -4.8, -5.0, -5.3, -5.3 (TBS).
HRMS (ESI+): m/z calcd. for C31H65N2O7Si4 (M+H)+ 689.3869, found
689.3879.
1
methyl-2,4(1H,3H)-pyrimidinedione (7e). 101 mg, 69%, gummy solid; H
NMR (400 MHz, CDCl3) δ 9.24 (s, 1H,H-9),), 7.48 (d, J = 1.0 Hz, 0.16H, H-
12(α-nucleoside), 7.40 – 7.28 (m, 16H, H-12(β-nucleoside), aromatic),
7.21 (s, 1H, aromatic), 7.16 – 7.09 (m, 2H, aromatic), 6.12 (d, J = 2.9 Hz,
0.16H, H-1(α-nucleoside)), 5.68 (d, J = 6.3 Hz, 1H, H-1(β-nucleoside)),
4.93 (q, J = 11.5 Hz, 2H, OBn), 4.80 (d, J = 10.8 Hz, 1H, OBn), 4.64-4.54
(
m, 4H, OBn), 4.47 (s, 0.16H), 4.35 (t, J = 2.9 Hz, 0.16H), 4.17 (q, J = 7.1
Hz, 0.33H).3.83 – 3.67 (m, 7H, H-2, H-3, H-4, H-5, H-6a, H-6b), 2.01 (d, J
0.7 Hz, 3H, methyl(β-nucleoside)), 1.90 (d, J = 0.5 Hz, 0.48H, methyl(α-
1
-{3',4',6'-Tri-O-(tert-butyldimethylsilyl)-2-O-trimethylsilyl-β-D-
glucopyranosyl}-5-methyl-2,4(1H,3H)-pyrimidinedione (7j). 115 mg,
=
1
8
1
4%, gummy solid; H NMR (400 MHz, CDCl3) δ 9.13 (s, 1H, H-9), 7.41 (s,
H, H-12), 6.01 (d, J = 2.0 Hz, 1H, H-1), 4.17 (d, J = 5.0 Hz, 1H, H-5), 3.96
nucleoside)), 0.03 (s, 9H, TMS(β-nucleoside)), 0.01 (s, 1.29H, TMS(α-
nucleoside)). 13C NMR (101 MHz, CDCl3) δ 163.5 (C-10), 150.8 (C-8),
(s, 1H, H-3), 3.91 (dd, J = 10.7, 4.2 Hz, 1H, H6a), 3.82 (d, J = 2.4 Hz, 1H,
1
1
1
38.5, 137.8 (quaternary aromatic), 135.4 (C-12), 128.6, 128.5, 128.4,
28.3, 127.9, 127.9, 127.8, 127.5, 127.1 (aromatic), 111.7 (C-11), 85.8 (C-
), 77.6 (C-5), 77.5 (OBn), 75.5 (C-3, OBn), 75.1 (OBn), 73.8 (C-4), 73.5
H-2), 3.77 (dd, J = 10.6, 6.9 Hz, 1H, H-6b), 3.67 (d, J = 5.3 Hz, 1H, H-4),
1
.94 (s, 3H, methyl), 0.92 (d, J = 3.7 Hz, 18H, TBS), 0.90 (s, 9H, TBS),
.16 (s, 3H, TBS), 0.13 – 0.09 (m, 11H, TBS), 0.06 (d, J = 3.0 Hz, 4H,
0
(C-2), 68.4 (C-6), 12.4 (methyl), 0.3 (TMS). HRMS (ESI+): m/z calcd. for
TBS), 0.00 (s, 9H, TMS). 13C NMR (101 MHz, CDCl3) δ 164.3 (C-10), 149.9
+
C35H43N2O7Si (M+H) 631.2840, found 631.2819.
(
(
C-8), 138.6 (C-12), 108.5 (C-11), 80.1 (C-5), 77.9 (C-1), 74.5 (C-2), 70.6
C-4), 69.2 (C-3), 62.9 (C-6), 25.9, 25.8, 25.7, 18.3, 17.9, 17.8 (TBS), 12.4
1
-{3',4',6'-Tri-O-(benzyl)-2-O-trimethylsilyl-β-D-glucopyranosyl}-5-
(methyl), -0.4 (TMS), -4.1, -4.5, -4.8, -4.9, -5.2, -5.3 (TBS). HRMS (ESI+):
m/z calcd. for C32H67N2O7Si4 (M+H) 703.4025, found 703.4037.
1
+
bromo-2,4(1H,3H)-pyrimidinedione (7f). 107 mg, 66%, gummy solid; H
NMR (400 MHz, CDCl3) δ 8.78 (s, 1H, NH), 7.67 (s, 1H, H-12), 7.38 – 7.26
(m, 16H, aromatic), 7.12 – 7.07 (m, 2H, aromatic), 6.06 (d, J = 2.7 Hz,
1-{3',4',6'-Tri-O-(tert-butyldimethylsilyl)-2-O-trimethylsilyl-β-D-
0
4
.10H, H-1(α-nucleoside)), 5.60 (d, J = 7.3 Hz, 1H, H-1(β-nucleoside)),
.89 (dd, J = 27.5, 11.5 Hz, 2H, OBn), 4.74 (d, J = 10.7 Hz, 1H, OBn), 4.54
glucopyranosyl}-5-chloro-2,4(1H,3H)-pyrimidinedione (7k). 113 mg,
1
80%, gummy solid; H NMR (400 MHz, CDCl3) δ 9.85 (s, 1H, H-9), 7.79 (s,
1H, H-12), 6.00 (d, J = 2.4 Hz, 1H, H-1), 4.18 (dd, J = 10.2, 6.4 Hz, 1H, H-
5), 4.02 (s, 1H, H-2), 3.90 (dd, J = 10.8, 3.9 Hz, 1H, H-6a), 3.83 (d, J = 2.6
(q, J = 12.1 Hz, 4H, OBn), 3.75 – 3.62 (m, 6H, H-2, H-3, H-4, H-5, H-6a,
H-6b), 0.00 (s, 9H, TMS(β-nucleoside)), -0.01 (s, 0.88H, TMS(α-
nucleoside)). 13C NMR (101 MHz, CDCl3) δ 158.3 (C-10), 149.6 (C-8),
Hz, 1H, H-3), 3.76 (dd, J = 10.8, 7.0 Hz, 1H, H-6b), 3.67 (d, J = 5.8 Hz, 1H,
H-4), 0.91 (d, J = 3.8 Hz, 18H, TBS), 0.90 (s, 9H, TBS), 0.17 (s, 3H, TBS),
1
1
39.3 (C-12), 138.3, 137.6, 137.6 (quaternary aromatic), 128.5, 128.5,
28.4, 128.0, 127.9, 127.8, 127.7, 127.5, 127.0 (aromatic), 97.6 (C-11),
0.13 – 0.09 (m, 11H, TBS), 0.07 (d, J = 1.6 Hz, 4H, TBS), 0.03 (s, 9H,
7
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