Nucleoside Diphosphate Glycopyranoses
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solid (89.0 mg, 56%). [a] = +88 (c=0.1, H2O); 1H NMR (400 MHz,
1H), 6.37 (t, J=6.9 Hz, 1H), 5.58 (dd, J=6.8, 3.7 Hz, 1H), 4.63–4.66 (m,
1H), 4.30 (q, J=6.6 Hz, 1H), 4.18–4.23 (m, 3H), 3.93 (dd, J=10.3,
3.4 Hz, 1H), 3.84 (d, J=3.2 Hz, 1H), 3.76 (td, J=10.3, 3.3 Hz, 1H), 2.34–
2.44 (m, 2H), 1.94 (d, J=1.0 Hz, 3H), 1.23 ppm (d, J=6.6 Hz, 3H);
13C NMR: (101 MHz, D2O): d = 168.3, 151.8, 137.4, 111.8, 95.5 (d, J=
7.2 Hz), 85.5 (d, J=8.9 Hz), 85.1, 71.9, 71.1, 69.6, 68.3 (d, J=8.5 Hz),
68.0, 65.5 (d, J=5.8 Hz), 38.6, 15.5, 11.8 ppm; 31P NMR: (162 MHz,
D2O): d = À12.79 (d, J=20.7 Hz, Pa), À11.36 ppm (d, J=20.3 Hz, Pb);
20
546
D2O): d=7.76 (d, J=1.0 Hz, thymine-CH3, 1H), 6.36 (dd, J=6.5, 6.5 Hz,
H-1’, 1H), 5.65 (dd, J=7.3, 3.8 Hz, H-1, 1H), 4.63 (m, H-3’, 1H,), 4.19–
4.20 (m, H-2, H-4’, H-5’, 4H), 4.04 (d, J=3.0 Hz, H-4, 1H), 3.93 (dd, J=
10.3 Hz, 3JHH =3.0 Hz, H-3, 1H), 3.71–3.83 (m, H-5, H-6, 3H), 3.21 (q,
J=7.4 Hz, 2ꢃCH2-NEt3, 12H), 2.37–2.44 (m, H-2’, 2H), 1.94 (d, J=
1.0 Hz, thymine-CH3, 3H), 1.29 ppm (t, J=7.4 Hz, 2ꢃCH3-NEt3, 18H,);
13C NMR (101 MHz, D2O): d=166.6, 151.8, 137.4, 111.8, 95.8 (d, J=
6.6 Hz), 95.8 (d, J=6.6 Hz), 85.4 (d, J=8.8 Hz), 85.1, 71.9, 71.0, 69.4,
69.2, 68.5 (d, J=8.1 Hz), 65.5 (d, J=5.6 Hz), 61.1, 46.7, 38.6, 11.7,
8.3 ppm; 31P NMR (162 MHz, D2O): d=À12.66 (d, J=20.9 Hz, Pa),
À11.20 ppm (d, J=20.9 Hz, Pb); IR: n˜ = 3278, 1666, 1471, 1238, 1175,
1040, 940, 888, 819, 766 cmÀ1; MS (HR-ESI): m/z: calcd for 563.0685;
found: 563.0671 [MÀH]À.
IR: n˜ = 3228, 1662, 1474, 1233, 1172, 1045, 935, 886, 811, 750, 666 cmÀ1
MS (HR-ESI): m/z: calcd for 547.0741 [MÀH]À; found: 547.0712.
;
Thymidine diphosphate-b-l-fucose 27: According to GP B the reaction
was conducted with 1a (60.0 mg, 0.12 mmol) and 2,3,4,6-tetra-O-acetyl-b-
l-fucose-1-phosphate (2gb; 100 mg, 0.24 mmol) within a reaction time of
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546
36 h in DMF (5 mL) to afford a yellow solid (53.0 mg, 75%). [a]
=
1
Thymidine diphosphate-b-d-galactose 23: According to GP A, the reac-
tion was conducted with 1a (85.0 mg, 0.18 mmol) and 2,3,4,6-tetra-O-
acetyl-b-d-galactopyranosyl-1-phosphate (2bb; 105 mg, 0.19 mmol)
À108 (c=0.2, H2O); H NMR (400 MHz, D2O): d = 7.74 (s, 1H), 6.35 (t,
J=6.9 Hz, 1H), 4.92 (t, J=8.0 Hz, 1H), 4.61–4.65 (m, 1H), 4.18 (d, J=
4.4 Hz, 3H), 3.82 (q, J=6.3 Hz, 1H), 3.75 (d, J=3.1 Hz, 1H), 3.70 (dd,
J=10.0, 3.4 Hz, 1H), 3.57 (dd, J=9.9, 7.8 Hz, 1H), 2.37–2.41 (m, 2H),
1.92 (s, 3H), 1.25 ppm (d, J=6.4 Hz, 3H); 13C NMR (101 MHz, D2O): d
= 166.7, 151.8, 137.3, 111.8, 98.4 (d, J=6.0 Hz), 85.3 (d, J=9.1 Hz), 85.0.
72.5, 71.4, 71.2, 71.1, 71.0, 65.5 (d, J=5.6 Hz), 38.6, 15.4, 11.7 ppm;
31P NMR (162 MHz, D2O): d = À12.98 (d, J=21.2 Hz, Pa), À11.33 ppm
(d, J=21.09 Hz, Pb); IR: n˜ = 3228, 1662, 1474, 1234, 1172, 1011, 935,
886, 750, 886, 750 cmÀ1; MS (HR-ESI): m/z: calcd for 547.0741 [MÀH]À;
found: 547.0734.
within a reaction time of 5 h at 508C in DMF (4 mL) to afford a colorless
20
solid (85.0 mg, 55%). [a] = À148 (c=0.1, H2O); 1H NMR (400 MHz,
546
D2O): d=7.71 (d, J=1.0 Hz, thymine-CH3, 1H), 6.31 (dd, J=6.6, 6.6 Hz,
H-1’, 1H), 4.91 (dd, J=7.6, 7.6 Hz, H-1, 1H), 4.58–4.60 (m, H-3’, 1H),
4.13–4.14 (m, H-4’, H-5’, 3H), 3.87 (d, J=3.3 Hz, H-2, 1H), 3.74–3.80 (m,
H-3, H-5, 2H), 3.70 (dd, J=3.0, 10.3 Hz, H-6, 1H), 3.63–3.67 (m, H-4,
1H), 3.57 (dd, J=7.6, 10.3 Hz, H-6, 1H), 3.15 (q, J=7.3 Hz, 2ꢃCH2-
NEt3, 12H), 2.27–2.39 (m, H-2’, 2H), 1.88 (s, J=1.0 Hz, thymine-CH3,
3H), 1.23 ppm (t, J=7.3 Hz, 2ꢃCH3-NEt3, 18H); 13C NMR: (101 MHz,
D2O): d=166.9, 152.1, 137.7, 112.1, 98.9 (d, J=5.6 Hz), 85.8 (d, J=
9.2 Hz), 85.4, 76.2, 72.7, 71.6 (d, J=82. Hz), 69.0, 65.9 (d, J=5.6 Hz),
61.6, 47.0, 39.0, 12.0, 8.6 ppm; 31P NMR (162 MHz, D2O): d=À13.24 (d,
J=20.7 Hz, Pa), À11.75 ppm (d, J=20.7 Hz, Pb); IR: n˜ = 3222, 1660,
1473, 1234, 1169, 1010, 933, 798, 749 cmÀ1; MS (HR-ESI): m/z: calcd for
563.0685 [MÀH]À; found: 563.0673.
Cytidine diphosphate-a-d-glucose 28: According to GP B the reaction
was conducted with 5-nitro-cycloSal-N4-Ac-2’,3’-O-Ac-cytidine-mono-
phosphate (1c; 55.0 mg, 0.09 mmol) and 2aa (70.0 mg, 0.27 mmol) (dif-
ferent from the GP B with 3.0 instead of 2.0 equivalents of glycosyl-1-
phosphate) within a reaction time of 24 h afforded a colorless solid
20
546
1
(52.0 mg, 75%). [a] = À158 (c=0.1, H2O); H NMR (400 MHz, D2O):
d = 8.09 (d, J=7.7 Hz, 1H), 6.01 (d, J=7.7 Hz,1H), 5.82 (dd, J=5.0,
5.0 Hz, 1H), 5.62 (dd, J=7.4, 3.4, 1H), 3.74–3.82 (m, 7H), 3.49–3.53 (m,
2H), 3.40–3.45 (m, 2H), 3.22 (q, J=7.3 Hz, 12H), 1.30 ppm (t, J=7.3 Hz,
18H); 13C NMR (101 MHz, D2O): d = 163.5, 154.2, 142.6, 97.8 (d, J=
5.9 Hz), 96.2, 89.3, 83.0 (d, J=9.1 Hz), 76.5, 75.3, 74.3, 73.6, 69.5, 69.3 (d,
J=8.1 Hz), 64.7 (d, J=5.6 Hz), 60.8, 46.7, 8.3 ppm; 31P NMR (162 MHz,
D2O): d = À14.00 (d, J=20.9 Hz, Pa), À12.42 ppm (d, J=20.9 Hz, Pb);
Thymidine diphosphate-a-d-mannose 24: According to GPA, the reac-
tion was conducted with 1a (100 mg, 0.21 mmol) and 2,3,4,6-tetra-O-
acetyl-a-d-mannopyranosyl-1-phosphate (2ca) (133 mg, 0.25 mmol)
within a reaction time 4 h at 508C in DMF (5 mL) to afford a colorless
20
solid (80.0 mg, 49%). [a] = +258 (c=0.1, H2O); 1H NMR (400 MHz,
546
D2O): d=7.71 (d, J=0.8 Hz, 1H), 6.30 (dd, J=6.8, 6.8 Hz, 1H), 5.45 (d,
J=6.8 Hz, 1H), 4.56–4.57 (m, 1H), 4.13 (m, 3H), 3.99–4.00 (m, 1H), 3.86
(dd, J=3.3, 12.3 Hz, 1H), 3.77–3.81 (m, 2H), 3.71 (dd, J=5.3, 12.3 Hz,
1H), 3.59–3.65 (m, 1H), 3.14 (q, J=7.3 Hz, 12H), 2.26–2.37 (m, 2H),
1.87 (s, 3H), 1.22 ppm (t, J=7.3 Hz, 18H); 13C NMR (101 MHz, D2O):
d=168.3, 151.8, 137.4, 111.8, 96.5 (d, J=4.4 Hz), 85.5 (d, J=8.8 Hz), 85.1,
73.7, 71.1, 70.3 (d, J=8.8 Hz), 69.9, 66.5, 65.5 (d, J=5.9 Hz), 60.9, 46.7,
38.7, 11.7, 8.3 ppm; 31P NMR (162 MHz, D2O): d=À13.99 (d, J=18.6 Hz,
Pa), À11.87 ppm (d, J=18.6 Hz, Pb); IR: n˜ = 3232, 1666, 1472, 1239,
1170, 1041, 935, 884, 87, 747 cmÀ1; MS (HR-ESI): m/z: calcd for 563.0685
[MÀH]À; found: 563.0667.
IR (KBr): n˜
640 cmÀ1
564.0628.
= 3430, 2924, 2348, 1654, 1240, 1153, 984, 807, 746,
;
MS (HR-ESI): m/z: calcd for 564.0637 [MÀH]À; found:
Cytidine diphosphate-b-d-glucose 29: According to GP B the reaction
was conducted with 1c (110 mg, 0.19 mmol) and 2ab (220 mg, 0.41 mmol)
within a reaction time of 24 h in DMF (3.5 mL) to afford a colorless solid
20
546
1
(97.0 mg, 67%). [a] = +208 (c=0.1, H2O); H NMR (400 MHz, D2O):
d = 8.06 (d, J=7.7 Hz, 1H), 6.20 (d, J=7.7 Hz, 1H), 5.97 (dd, J=4.6,
4.6 Hz, 1H), 5.00 (dd, J=5.6, 5.2 Hz, 1H), 4.21–4.40 (m, 5H), 3.89 (dd,
J=12.4, 2.1 Hz, 1H), 3.67–3.72 (m, 1H), 3.47–3.53 (m, 2H), 3.35–3.40 (m,
2H), 3.19 (q, J=7.3 Hz, 12H), 1.27 ppm (t, J=7.3 Hz, 18H); 13C NMR
(101 MHz, D2O): d = 163.5, 154.2, 142.6, 97.8 (d, J=6.1 Hz), 96.2, 89.3,
83.0 (d, J=9.2 Hz), 76.5, 75.3, 74.3, 73.6, 69.5, 69.3 (d, J=7.3 Hz), 64.7 (d,
J=5.6 Hz), 60.8, 46.7, 8.3 ppm; 31P NMR (162 MHz, D2O): d = À11.97
(d, J=20.6 Hz, Pa), À10.26 ppm (d, J=20.6 Hz, Pb); IR (KBr): n˜ = 3422,
2923, 2979, 1654, 1550, 1458, 1400, 1240, 1125, 985 cmÀ1; MS (HR-ESI):
m/z: calcd for 564.0637 [MÀH]À; found: 564.0610.
Thymidine diphosphate-b-d-fucose 25: According to GP B the reaction
was conducted with 1a (57.0 mg, 0.11 mmol) and 2,3,4,6-tetra-O-acetyl-b-
d-fucose-1-phosphate 2 fb (95.0 mg, 0.23 mmol) within a reaction time of
20
546
36 h in DMF (5 mL) to afford a colorless solid (58.0 mg, 81%). [a]
=
1
À78.68 (c=0.1, H2O); H NMR (400 MHz, D2O): d = 7.76 (d, J=1.2 Hz,
1H), 6.37 (t, J=7.0 Hz, 1H), 4.95 (t, J=8.0 Hz, 1H), 4.63–4.65 (m, 1H),
4.20 (d, J=4.8 Hz, 3H), 3.84 (q, J=6.5 Hz, 1H), 3.76 (d, J=3.1 Hz, 1H),
3.70 (dd, J=10.0, 3.5 Hz, 1H), 3.58 (dd, J=9.9, 7.7 Hz, 1H), 2.39 (dd, J=
6.1 Hz, 2H), 1.95 (d, J=1.0 Hz, 3H), 1.28 ppm (d, J=6.5 Hz, 3H);
13C NMR (101 MHz, D2O): d = 166.6, 151.8, 137.4, 111.8, 98.4 (d, J=
6.0 Hz), 85.4 (d, J=9.1 Hz), 85.0. 72.4, 71.4, 71.2, 71.1, 71.0, 65.5 (d, J=
5.6 Hz), 38.7, 15.5, 11.7 ppm; 31P NMR (162 MHz, D2O): d = À12.79 (d,
J=19.9 Hz, Pa), À11.32 ppm (d, J=21.1 Hz, Pb); IR: n˜ = 3219, 1662,
1476, 1234, 1171, 1011, 936, 812, 751 cmÀ1; MS (HR-ESI): m/z: calcd for
547.0741 [MÀH]À; found: 547.0706.
Cytidine diphosphate-b-d-galactose 30: According to GP B the reaction
was conducted with 1c (61.0 mg, 0.11 mmol) and 2bb (110 mg,
0.21 mmol) within a reaction time of 24 h in DMF (3 mL) to afford a col-
20
546
orless solid (61.3 mg, 76%). [a]
=
+88 (c=0.1, H2O); 1H NMR
(400 MHz, D2O): = d 8.08 (d, J=7.7 Hz, 1H), 6.22 (d, J=7.7 Hz, 1H),
5.99 (d, J=4.0 Hz, 1H), 4.96 (dd, J=7.8, 7.1 Hz, 1H), 4.39–4.36 (m, 1H),
4.19–4.37 (m, 4H), 3.92 (d, J=3.2 Hz, 1H), 3.78–3.84 (m, 1H), 3.68–3.76
(m, 2H), 3.60–3.64 (m, 2H), 3.20 (q, J=7.3 Hz, 12H), 1.28 ppm (t, J=
7.3 Hz, 18H); 13C NMR (101 MHz, D2O): d = 163.7, 154.4, 142.9, 98.9
(d, J=6.2 Hz), 96.5, 89.6, 83.4 (d, J=9.2 Hz), 76.2, 74.7, 71.6 (d, J=
8.5 Hz), 69.7, 62.7, 69.0 (d, J=8.5 Hz), 61.6 (d, J=5.4 Hz), 47.0, 8.6 ppm;
31P NMR (162 MHz, D2O): d = À13.02 (d, J=20.5 Hz, Pa), À11.57 ppm
(d, J=20.5 Hz, Pb); IR (KBr): n˜ = 3422, 2680, 2347, 1725, 1655, 1477,
Thymidine diphosphate-a-l-fucose 26: According to GP B the reaction
was conducted with 1a (53.0 mg, 0.11 mmol) and 2,3,4,6-tetra-O-acetyl-b-
l-fucose-1-phosphate (2ga; 89.0 mg, 0.21 mmol) within a reaction time of
20
546
36 h in DMF (5 mL) to afford a colorless solid (41.0 mg, 65%). [a]
=
À38 (c=0.1, H2O); 1H NMR: (400 MHz, D2O): d = 7.76 (d, J=1.1 Hz,
Chem. Eur. J. 2009, 15, 7656 – 7664
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
7661