W. Hirose, K. Sato, A. Matsuda
FULL PAPER
(125 MHz, [D6]DMSO): δ = 161.6, 160.7, 150.3, 149.3, 141.5,
136.4, 128.7, 126.6, 123.1, 121.6, 106.6, 88.0, 85.9, 70.2, 61.0,
40.5 ppm. ESI-MS (LR): m/z = 396 [M + H]+. C16H14ClN3O5S
(395.82): calcd. C 48.55, H 3.57, Cl 8.96, N 10.62, S 8.16; found C
48.15, H 3.76, Cl 8.67, N 10.39, S 7.77.
412 [M + Na]+. C18H19N3O5S·1/5H2O: calcd. C 55.01, H 4.98, N
10.69, S 8.16; found C 55.00, H 4.93, N 10.49, S 8.03.
5-(6-Methoxybenzothiazol-2-yl)-2Ј-deoxyuridine (4h): Compound
4h (64 mg, 0.16 mmol, 82%, as a yellow solid) was obtained from
dfoU (51 mg, 0.20 mmol), 3h (62 mg, 0.20 mmol), (Ϯ)-DTT (31 mg,
0.20 mmol), Sc(OTf)3 (10 mg, 0.020 mmol), and aqueous H2O2
(35%, 13 μL, 0.20 mmol) as described for the synthesis of 4c. The
sample for elemental analysis and fluorescence experiments was ob-
tained by crystallization from aq. EtOH, as a yellow crystal (228 °C
colored). UV: λmax (ε, m–1 cm–1) = 351 (14300) (aq. 100 mm HCl),
336 (14600) (10 mm phosphate buffer, pH 7.0), 335 (17600) (aq.
5-(6-Bromobenzothiazol-2-yl)-2Ј-deoxyuridine (4e): Compound 4e
(130 mg, 0.29 mmol, 97%, as a yellow solid) was obtained from
dfoU (77 mg, 0.30 mmol), 3e (120 mg, 0.30 mmol), (Ϯ)-DTT
(93 mg, 0.60 mmol), Sc(OTf)3 (15 mg, 0.030 mmol), and aqueous
H2O2 (35%, 58 μL, 0.90 mmol) as described for the synthesis of 4a.
The sample for fluorescence experiments was obtained by crystalli-
zation from aq. EtOH as a yellow crystal (255 °C colored). UV:
λmax (ε, m–1 cm–1) = 333 (16300) (aq. 100 mm HCl), 330 (16500)
(10 mm phosphate buffer, pH 7.0), 331 (20300) (aq. 100 mm NaOH)
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100 mm NaOH) nm. H NMR (500 MHz, [D6]DMSO): δ = 11.99
(s, 1 H, NH), 9.01 (s, 1 H, 6-H), 7.83 (d, J = 9.2 Hz, 1 H, 4ЈЈ-H),
7.63 (d, J = 2.3 Hz, 1 H, 7ЈЈ-H), 7.08 (dd, J = 9.2, 2.3 Hz, 1 H, 5ЈЈ-
H), 6.19 (t, J = 6.3 Hz, 1 H, 1Ј-H), 5.31 (d, J = 4.6 Hz, 1 H, OH-
3Ј), 5.07 (t, J = 4.6 Hz, 1 H, OH-5Ј), 4.29 (m, 1 H, 3Ј-H), 3.88 (m,
1 H, 4Ј-H), 3.82 (s, 3 H, CH3O), 3.63 (m, 2 H, 5Ј-H), 2.25 (m, 2
H, 2Ј-H) ppm. 13C NMR (125 MHz, [D6]DMSO): δ = 161.5, 156.9,
156.8, 149.4, 146.0, 140.3, 136.3, 122.5, 115.6, 107.2, 104.3, 87.9,
85.7, 70.3, 61.1, 55.7, 40.4 ppm. ESI-MS (LR): m/z = 414 [M +
Na]+. C17H17N3O6S·2/5H2O: calcd. C 51.22, H 4.53, N 10.54, S
8.04; found C 51.18, H 4.37, N 10.26, S 7.80.
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nm. H NMR (400 MHz, [D6]DMSO): δ = 12.06 (br. s, 1 H, NH),
9.16 (s, 1 H, 6-H), 8.36 (d, J = 1.8 Hz, 1 H, 7ЈЈ-H), 7.87 (d, J =
8.6 Hz, 1 H, 4ЈЈ-H), 7.63 (dd, J = 8.6, 1.8 Hz, 1 H, 5ЈЈ-H), 6.18 (t,
J = 6.3 Hz, 1 H, 1Ј-H), 5.32 (d, J = 4.1 Hz, 1 H, OH-3Ј), 5.11 (t,
J = 4.5 Hz, 1 H, OH-5Ј), 4.29 (m, 1 H, 3Ј-H), 3.90 (m, 1 H, 4Ј-H),
3.65 (m, 2 H, 5Ј-H), 2.26 (m, 2 H, 2Ј-H) ppm. 13C NMR (100 MHz,
[D6]DMSO): δ = 161.6, 160.7, 150.6, 149.3, 141.6, 136.9, 129.3,
124.5, 123.5, 116.8, 106.6, 88.0, 85.9, 70.2, 61.0, 40.5 ppm. ESI-MS
(LR): m/z = 438, 440 [M – H]–. ESI-MS (HR): calcd. for
C16H13BrN3O5S 437.9768; found 437.9781.
5-(5,6-Dimethoxybenzothiazol-2-yl)-2Ј-deoxyuridine (4i): Com-
pound 4i (95 mg, 0.23 mmol, 75%, as a yellow-green solid) was
obtained from dfoU (77 mg, 0.30 mmol), 3i (110 mg, 0.30 mmol),
(Ϯ)-DTT (46 mg, 0.30 mmol), Sc(OTf)3 (15 mg, 0.030 mmol), and
aqueous H2O2 (35%, 19 μL, 0.30 mmol) as described for the syn-
thesis of 4c. The sample for elemental analysis and fluorescence
experiments was obtained by crystallization from aq. EtOH as a
yellow–green crystal (236 °C colored). UV: λmax (ε, m–1 cm–1) = 368
(15900) (aq. 100 mm HCl), 351 (16600) (10 mm phosphate buffer,
pH 7.0), 345 (20000) (aq. 100 mm NaOH) nm. 1H NMR (500 MHz,
[D6]DMSO): δ = 11.95 (s, 1 H, NH), 8.98 (s, 1 H, 6-H), 7.60, 7.45
(each s, each 1 H, 4ЈЈ-H and 7ЈЈ-H), 6.19 (t, J = 6.3 Hz, 1 H, 1Ј-
H), 5.30 (d, J = 4.6 Hz, 1 H, OH-3Ј), 5.07 (t, J = 4.6 Hz, 1 H, OH-
5Ј), 4.28 (m, 1 H, 3Ј-H), 3.87 (d, J = 2.8 Hz, 1 H, 4Ј-H), 3.83, 3.81
(each s, each 3 H, CH3Oϫ2), 3.63 (m, 2 H, 5Ј-H), 2.23 (m, 2 H,
2Ј-H) ppm. 13C NMR (125 MHz, [D6]DMSO): δ = 161.6, 157.2,
149.6, 149.3, 148.0, 146.1, 140.0, 127.1, 107.7, 104.1, 103.3, 88.0,
85.7, 70.5, 61.4, 56.1, 55.9, 39.9 ppm. ESI-MS (LR): m/z = 420
[M – H]–. C18H19N3O7S·1/2H2O: calcd. C 50.23, H 4.68, N 9.76, S
7.45; found C 50.16, H 4.68, N 9.52, S 7.26.
5-(6-Iodobenzothiazol-2-yl)-2Ј-deoxyuridine (4f): Compound 4f
(96 mg, 0.20 mmol, 66%, as a white solid) was obtained from dfoU
(77 mg, 0.30 mmol), 3f (150 mg, 0.30 mmol), (Ϯ)-DTT (230 mg,
1.5 mmol), Sc(OTf)3 (15 mg, 0.030 mmol), and aqueous H2O2
(35%, 96 μL, 1.5 mmol) as described for the synthesis of 4c. The
sample for elemental analysis and fluorescence experiments was ob-
tained by crystallization from aq. EtOH as a white crystal (262 °C
colored). UV: λmax (ε, m–1 cm–1) = 332 (10100) (aq. 100 mm HCl),
332 (10000) (10 mm phosphate buffer, pH 7.0), 332 (24000) (aq.
1
100 mm NaOH) nm. H NMR (500 MHz, [D6]DMSO): δ = 12.05
(br. s, 1 H, NH), 9.15 (s, 1 H, 6-H), 8.49 (s, 1 H, 7ЈЈ-H), 7.77, 7.73
(each d, J = 8.6 Hz, each 1 H, 4ЈЈ-H and 5ЈЈ-H), 6.18 (t, 1 H, 1Ј-
H, J = 6.3 Hz), 5.32 (d, J = 4.0 Hz, 1 H, OH-3Ј), 5.10 (t, J =
4.0 Hz, 1 H, OH-5Ј), 4.29 (m, 1 H, 3Ј-H), 3.90 (m, 1 H, 4Ј-H), 3.64
(m, 2 H, 5Ј-H), 2.26 (m, 2 H, 2Ј-H) ppm. 13C NMR (100 MHz,
[D6]DMSO): δ = 161.6, 160.4, 151.0, 149.3, 141.6, 137.3, 134.8,
130.2, 123.7, 106.6, 89.1, 88.0, 85.9, 70.2, 61.0, 40.5 ppm. ESI-MS
(LR): m/z = 486 [M – H]–. C16H14IN3O5S (487.27): calcd. C 39.44,
H 2.90, N 8.62, S 6.58; found C 39.51, H 2.90, N 8.56, S 6.58.
5-(4,6-Dimethoxybenzothiazol-2-yl)-2Ј-deoxyuridine (4j): Com-
pound 4j (85 mg, 0.20 mmol, 67%, as a pale pink solid) was ob-
tained from dfoU (77 mg, 0.30 mmol), 3j (110 mg, 0.30 mmol), (Ϯ)-
DTT (230 mg, 1.5 mmol), Sc(OTf)3 (15 mg, 0.030 mmol), and
5-(6-Ethylbenzothiazol-2-yl)-2Ј-deoxyuridine (4g): Compound 4g
(69 mg, 0.18 mmol, 59%, as a yellow solid) was obtained from dfoU
(77 mg, 0.30 mmol), 3g (91 mg, 0.30 mmol), (Ϯ)-DTT (230 mg, aqueous H2O2 (35%, 140 μL, 2.3 mmol) as described for the syn-
1.5 mmol), Sc(OTf)3 (15 mg, 0.030 mmol), and aqueous H2O2 thesis of 4c. The sample for elemental analysis and fluorescence
(35%, 96 μL, 1.5 mmol) as described for the synthesis of 4c. The
sample for elemental analysis and fluorescence experiments was ob-
tained by crystallization from aq. EtOH as a white crystal
(250 °C colored). UV: λmax (ε, m–1 cm–1) = 345 (9100) (aq. 100 mm
experiments was obtained by crystallization from aq. EtOH as a
yellow crystal (218 °C colored). UV: λmax (ε, m–1 cm–1) = 345
(12900) (aq. 100 mm HCl), 341 (12000) (10 mm phosphate buffer,
pH7.0),339(15500)(aq.100 mmNaOH)nm.1HNMR(500 MHz,[D6]-
HCl), 331 (8300) (10 mm phosphate buffer, pH 7.0), 332 (15600) DMSO): δ = 11.98 (br. s, 1 H, NH), 8.79 (s, 1 H, 6-H), 7.19, 6.61
(aq. 100 mm NaOH) nm. 1H NMR (500 MHz, [D6]DMSO): δ =
(each d, J = 2.3 Hz, each 1 H, 5ЈЈ-H and 7ЈЈ-H), 6.16 (t, J = 6.9 Hz,
12.00 (br. s, 1 H, NH), 9.06 (s, 1 H, 6-H), 7.88 (s, 1 H, 7ЈЈ-H), 7.84 1 H, 1Ј-H), 5.32 (d, J = 4.6 Hz, 1 H, OH-3Ј), 4.97 (t, J = 5.2 Hz,
(d, J = 8.6 Hz, 1 H, 4ЈЈ-H), 7.34 (d, J = 8.6 Hz, 1 H, 5ЈЈ-H), 6.19 1 H, OH-5Ј), 4.26 (m, 1 H, 3Ј-H), 3.94 (s, 3 H,CH3O), 3.89 (dd, J
(t, J = 6.3 Hz, 1 H, 1Ј-H), 5.32 (d, J = 4.0 Hz, 1 H, OH-3Ј), 5.07 = 7.4, 4.0 Hz, 1 H, 4Ј-H), 3.81 (s, 3 H, CH3O), 3.59 (t, J = 4.6 Hz,
(t, J = 4.6 Hz, 1 H, OH-5Ј), 4.29 (dd, J = 4.0, 3.4 Hz, 1 H, 3Ј-H), 2 H, 5Ј-H), 2.25 (m, 2 H, 2Ј-H) ppm. 13C NMR (100 MHz, [D6]-
3.89 (d, J = 3.4 Hz, 1 H, 4Ј-H), 3.68 (m, 2 H, 5Ј-H), 2.73 (q, J =
7.4 Hz, 2 H, CH2CH3), 2.25 (m, 2 H, 2Ј-H), 1.24 (t, J = 7.4 Hz, 3
H, CH2CH3) ppm. 13C NMR (125 MHz, [D6]DMSO): δ = 161.5,
158.5, 149.9, 149.4, 140.8, 140.4, 135.0, 126.6, 121.6, 120.3, 107.1,
87.9, 85.7, 70.3, 61.1, 40.4, 28.2, 15.9 ppm. ESI-MS (LR): m/z =
DMSO): δ = 161.7, 158.1, 154.9, 153.0, 149.5, 139.7, 137.5, 136.7,
107.4, 98.6, 95.7, 88.1, 86.0, 70.6, 61.4, 56.3, 55.8, 40.2 ppm. ESI-
MS (LR): m/z = 420 [M – H]–. C18H19N3O7S·1/2H2O: calcd. C
50.23, H 4.68, N 9.76, S 7.45; found C 50.41, H 4.68, N 9.61, S
7.48.
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Eur. J. Org. Chem. 2011, 6206–6217