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C. Peyron et al. / Bioorganic Chemistry 33 (2005) 439–447
7.39 (d, 1H, J D7.8 Hz, H-4 or H-7 ind.), 7.62 (s, 1H, H-6), 7.64 (d, 2H, J D 7.2 Hz, H-
tol), 7.97 (d, 2H, J D7.2 Hz, H-tol), and 8.10 (d, 1H, J D 8.5Hz, H-7 or H-4 ind.). 13
C
NMR (CDCl3, 125 MHz) ꢀ (ppm) 21.45 (CH3), 21.60 (CH3), 27.83 (tBu), 38.28 (C-2Ј),
64.05 (C-5Ј), 74.90 (C-3Ј), 82.91 (C-4Ј), 83.64 (C-(CH3)3), 84.98 (C-1Ј), 110.62 (C-3
ind.), 112.20 (C-5), 115.32 (C-7 ind.), 120.54 (CH-ind.), 122.49 (CH-ind.), 124.45 (CH-
ind.), 125.86 (C-Ar), 126.11 (C-Ar), 128.42 (C-Ar), 128.86 (CH-tol), 128.97 (CH-tol),
129.17 (CH-tol), 129.70 (CH-tol), 130.26 (C-Ar), 134.78 (C-6), 136.86 (C-Ar), 144.05
(C-Ar), 144.47 (C-Ar), 149.47 (CO), 149.90 (CO), 161.48 (CO), 165.80 (CO), and
165.96 (CO). MS (ESI+) m/z D702 (MNa+).
2.1.1.4. 3Ј,5Ј-di-O-tolouyl-5-(indolyl-2)-2Ј-deoxyuridine (indole-deprotected side
product [5]). This compound was obtained as a side product in the palladium cou-
pling step. It is also an advanced intermediate in the synthesis of nucleoside 3h. 1H
NMR (CDCl3, 500 MHz) ꢀ (ppm) 2.16 (m, 1H, H-2Ј), 2.27 (s, 3H, CH3), 2.42 (s, 3H,
CH3), 2.75 (dd, 1H, J D 5.2 and 14.3 Hz, H-2Ј), 4.51 (m, 1H, H-4Ј), 4.72 (m, 2H, H-
5Ј), 5.54 (br d, 1H, J D 5.9 Hz, H-3Ј), 6.29 (br m, 1H, H-1Ј), 6.45 (s, 1H, H-3 ind.),
7.02 (t, 1H, J D 7.4 Hz, H-6 ind. or H-5 ind.), 7.09 (t, 1H, J D 7.8 Hz, H-5 ind. or H-6
ind.), 7.11 (d, 2H, J D 8.1 Hz, H-tol), 7.27 (d, 2H, J D 8.1 Hz, H-tol), 7.34 (d, 1H,
J D 7.9 Hz, H-4 ind. or H-7 ind.), 7.41 (d, 1H, J D 8.2 Hz, H-7 ind. or H-4 ind.), 7.92
(d, 2H, J D 7.9 Hz, H-tol), 7.97 (d, 2H, J D 8.2 Hz, H-tol), 8.05 (s, 1H, H-6), and 10.46
(s, 1H, NH). 13C NMR (CDCl3, 125 MHz) ꢀ (ppm) 21.55 (CH3), 21.70 (CH3), 38.36
(C-2Ј), 64.00 (C-5Ј), 74.65 (C-3Ј), 83.29 (C-4Ј), 85.90 (C-1Ј), 98.02 (C-3 ind.), 107.55
(C-5), 111.35 (CH-ind.), 119.75 (CH-ind.), 120.06 (CH-ind.), 121.81 (CH-ind.),
126.33 (2£ C-Ar), 127.75 (2£ C-Ar), 129.28 (CH-tol), 129.39 (CH-tol), 129.56 (CH-
tol), 129.80 (CH-tol), 134.28 (C-6), 136.14 (C-Ar), 144.51 (C-Ar), 144.56 (C-Ar),
149.13 (CO), 162.34 (CO), 166.02 (CO), and 166.39 (CO). MS (ESI+) m/z D 580
(MH)+, 603 (MNa)+.
2.1.1.5. 5-(N-tertbutoxycarbonylindolyl-2)-2Ј-deoxyuridine (5). To a solution of the
protected nucleoside 1h or 2h obtained above (0.5 mmol) in MeOH (5 mL) was
added K2CO3 (3 equiv.) and the reaction mixture was stirred over night at room
temperature. The mixture was Wltered and concentrated in vacuo. The residual oil
was puriWed on silica gel chromatography (CH2Cl2/MeOH: 95/5 to 90/10) to aVord
1
quantitative yield of pure product 5 as a foam. H NMR (CD3OD, 500 MHz) ꢀ
(ppm) 1.53 (s, 9H, tBu), 2.28 (m, 1H, H-2Ј), 2.31 (m, 1H, H-2Ј), 3.70 (dd, 1H, J D 3.3
and 11.9 Hz, H-5Ј), 3.78 (dd, 1H, J D 3.0 and 11.9 Hz, H-5Ј), 3.94 (m, 1H, H-4Ј), 4.41
(m, 1H, H-3Ј), 6.33 (t, 1H, J D 6.6 Hz, H-1Ј), 6.59 (s, 1H, H-3 ind.), 7.19 (t, 1H,
J D 7.5 Hz, H-5 or H-6 ind.), 7.26 (t, 1H, J D 7.5 Hz, H-6 or H-5 ind.), 7.52 (d, 1H,
J D 7.6 Hz, H-4 or H-7 ind.), 8.13 (d, 1H, J D 8.3 Hz, H-7 or H-4 ind.), 8.19 (s, 1H, H-
6). 13C NMR (CD3OD, 125 MHz) ꢀ (ppm) 28.43 (tBu), 42.05 (C-2Ј), 62.84 (C-5Ј),
72.39 (C-3Ј), 85.28 (C-(CH3)3), 87.07 (C-4Ј), 89.31 (C-1Ј), 111.86 (C-3 ind.), 112.60
(C-5), 116.44 (C-7 or C-4 ind.), 121.91 (C-4 or C-7 ind.), 124.05 (C-5 or C-6 ind.),
125.79 (C-6 or C-5 ind.), 130.43 (C-ind.), 133.20 (C-ind.), 138.81 (C-ind.), 139.17 (C-
6), 151.50 (CO), 152.34 (CO), and 164.97 (CO). MS (ESI+) m/z D 466 (MNa)+, 482
(MK)+.