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M. V. Skorobogatyi et al. / Tetrahedron 62 (2006) 1279–1287
4.4.1. 30,50-O-(Tetraisopropyldisiloxane-1,3-diyl)-5-(4-
benzoylphenoxypropyn-1-yl)-20-deoxyuridine (18a). The
title compound was purified in 20% EtOAc in toluene (v/v);
white amorphous solid (1.12 g, 79%); Rf 0.30 (30%
EtOAc in toluene). ESI MS: m/zZ727.6 [MCNa]C, calcd
for [C37H48N2O8Si2CNa]C727.9. ESI-TOF HRMS:
m/zZ705.3116 [MCH]C, 727.2923 [MCNa]C, calcd for
H-200); 6.72 (m, 1H, H-400); 5.94 (dd, 1H, J1 ,2 aZ7.6 Hz,
0
0
J1 ,2 bZ2.7 Hz, H-10); 4.88 (m, 2H, ArOCH2); 4.50 (m, 1H,
0
0
2
H-300); 4.04 (m, 1H, J5 a,5 bZ12.7 Hz, J4 ,5 aZ4.1 Hz,
0
0
0
0
2
0
0
0
0
H-50a); 3.92 (m, 1H, J5 a,5 bZ12.7 Hz, J4 ,5 bZ2.7 Hz,
H-5 b); 3.72 (m, 1H, H-40); 2.82 (m, 2H, H-600); 2.48–2.40
(m, 2H, H-20a, H-1600 (2JZ19.7 Hz, J15 ,16 Z8.5 Hz));
2.37–2.28 (m,002H, H-20b, H-1100); 2.19 (m,001H, H-900); 2.07
(m, 1H, H-16 ); 1.98 (m, 2H, H-700, H-15 ); 1.76 (m, 1H,
H-1200); 1.55 (m, 3H, H-800, H-1400, H-1500); 1.38 (m, 3H,
H-700, H-1100, H-1200); 1.10–0.94 (m, 28H, Pri); 0.83 (s, 3H,
H-1800). 13C NMR (DMSO-d6): 219.58 (C1700), 161.58 (C4),
155.35 (C300), 149.18 (C20)0, 144.05 (C6), 137.48 (C500),
132.47 (C1000), 126.22 (C1 ), 114.58 (C400), 112.38 (C2000),
97.41 (C5), 88.15 (CH2C^C), 84.38, 84.17 (C10, C4 ),
79.18 (CH2C^), 68.91 (C30), 60.87 (C50), 56.08 (CH2C
^), 49.63 (C1400), 47.34 (C1300), 43.4090 (C900), 38.61 (C20),
37.85 (C800), 35.39 (C1600), 31.39 (C12 ), 29.20 (C600), 26.06
(C700), 25.51 (C1100), 21.17 (C1500), 17.38, 17.23 (3C),
17.07, 16.91 (2C), 16.82 (CH3), 13.53 (C1800), 12.77, 12.50,
12.06, 11.96 (SiC).
00
00
[C37H48N2O8Si2CH]C705.3022,
[C37H48N2O8Si2C
1
Na]C727.2841. H NMR (DMSO-d6): 11.67 (s, 1H, NH);
7.90 (s, 1H, H-6); 7.76 (d, 2H, JZ8.7 Hz, H-300, H-500); 7.69
(m, 2H, 0H00 -2000, H-6000); 7.65 (m, 1H, H-4000); 7.55 (m, 2H, H-
3000, H-5 ); 7.16 (d, 2H, JZ8.7 Hz, H-200, H-600); 5.94 (dd,
1H, J1 ,2 aZ7.3 Hz, J1 ,2 bZ2.5 Hz, H-10); 5.10 (m, 2H,
0
0
0
0
2
^CCH2); 4.49 (m, 1H, H-30); 4.04 (m, 1H, J5 a,5 b
Z
Z
0
0
2
12.7 Hz, J4 ,5 aZ4.2 Hz, H-50a); 3.91 (m, 1H, J5 a,5 b
0
0
0
0
12.7 Hz, J4 ,5 bZ2.9 Hz, H-50b); 3.72 (m, 1H, H-40); 2.47
(m, 1H, H-20a); 2.32 (m, 1H, H-20b); 1.08–0.94 (m, 28H,
Pri). 13C NMR (DMSO-d6): 194.41 (PhCO), 161.57 (C4),
161.09 (C100), 149.18 (C2), 144.29 (C6), 137.70 (C1000),
0
0
132.20 (C4 ), 132.06 (2C, C3 , 5 ), 130.02 (C400), 129.28
000
000
00
000
00
000
(2C, C2000, 6 ), 128.49 (2C, C3 , 5 ), 114.72 (2C, C200, 6000),
97.15 (C5), 87.24 (CH2C^C), 84.38 (C40), 84.29 (C1 ),
79.96 (CH2C^), 68.80 (C30), 60.79 (C50), 56.62 (^CCH2),
38.59 (C20), 17.37, 17.21 (3C), 17.07, 16.91 (2C), 16.82
(CH3), 12.76, 12.47, 12.02, 11.95 (SiC).
4.4.4. 30,50-O-(Tetraisopropyldisiloxane-1,3-diyl)-5-
[(perylen-3-yl)methoxypropyn-1-yl]-20-deoxyuridine
(18d). The title compound was purified using a 10/50%
gradient of EtOAc in CHCl3 (v/v); yellow amorphous solid
(1.044 g, 66%); Rf 0.26 (30% EtOAc in CHCl3 (v/v)). ESI
MS: m/zZ811.7 [MCNa]C, calcd for [C45H52N2O7Si2C
Na]C812.1. ESI-TOF HRMS: m/zZ789.3338 [MCH]C,
811.3230 [MCNa]C, calcd for [C45H52N2O7Si2C
4.4.2. 30,50-O-(Tetraisopropyldisiloxane-1,3-diyl)-5-[4-
(triphenylmethyl)phenoxypropyn-1-yl]-20-deoxyuridine
(18b). The title compound was purified using a 0/20%
gradient of EtOAc in CHCl3 (v/v); white amorphous solid
(1.01 g, 60%); Rf 0.41 (30% EtOAc in CHCl3 (v/v)). ESI
MS: m/zZ865.8 [MCNa]C, calcd for [C49H58N2O7Si2C
Na]C866.2. ESI-TOF HRMS: m/zZ843.3909 [MCH]C,
calcd for [C49H58N2O7Si2CH]C843.3855. 1H NMR
(DMSO-d6): 11.65 (s, 1H, NH); 7.89 (s, 1H, H-6); 7.29
(m, 6H, Hd); 7.20 (m, 3H, He); 7.13 (m, 6H, Hc); 7.03 (m,
1
H]C789.3386, [C45H52N2O7Si2CNa]C811.3205. H NMR
(DMSO-d6): 11.68 (s, 1H, NH); 8.42–8.30 (m, 040 H, H-100,
H-600, H-700, H-1200); 7.99 (d, 1H, JZ8.2 Hz, H-4 ); 7.91 0(0s,
1H, H-6); 7.80 (d, 2H, J8,9ZJ10,11Z8.0 Hz, H-900, H-10 );
7.62–7.52 (m, 4H, H-200, H-500, H-8000, H-1100); 5.95 (dd, 1H,
0
0
0
0
J1 ,2 aZ7.4 Hz, J1 ,2 bZ2.6 Hz, H-1 ); 4.96 (s, 2H, ArCH2);
4.49 (m, 1H, H-30); 4.46 (s, 2H, ^CCH2); 4.04 (m, 1H,
2
J5 a,5 bZ12.7 Hz, J4 ,5 aZ4.3 Hz, H-50a); 3.90 (m, 1H,
0
0
0
0
0
0
2H), 6.92 (m, 2H) (Ha, Hb); 5.94 (dd, 1H, J1 ,2 aZ7.6 Hz,
J1 ,2 bZ2.8 Hz, H-10); 4.92 (m, 2H, ArOCH2); 4.49 (m, 1H,
2
J5 a,5 bZ12.7 Hz, J4 ,5 bZ2.7 Hz, H-50b); 3.71 (m, 1H,
0
0
0
0
0
0
2
H-300); 4.02 (m, 1H, J5 a,5 bZ12.8 Hz, J4 ,5 aZ4.3 Hz,
H-40); 2.46 (m, 1H, H-20a); 2.32 (m, 1H, H-20b); 1.04–0.93
(m, 28H, Pri). 13C NMR (DMSO-d6): 161.71 (C4), 149.23
(C2), 143.76 (C6), 1030 4.28 (C9a00), 133.11 (C300), 132.68
(C3a00), 130.88 (C6a ), 130.52 (C6b00), 130.3500 (C12a00),
0
0
0
0
2
0
0
0
0
H-50a); 3.91 (m, 1H, J5 a,5 bZ12.8 Hz, J4 ,5 bZ3.0 Hz,
H-5 b); 3.72 (m, 1H, H-40); 2.46 (m, 1H,† H-20a); 2.31 (m,
1H, H-20b); 1.07–0.96 (m, 28H, Pri). 13C NMR (DMSO-d6):
161.59 (C4), 155.53 (^CCH2OC), 149.18 (C2), 146.61
(3C, C6H4CC), 144.16 (C6), 139.08 (Ph3CC), 131.59 (2C,
Cb), 130.48 (6C, Cc), 127.68 (6C, Cd), 125.98 (3C, Ce),
113.85 (2C, Ca), 97.33 (C5), 87.88 (CH2C^C), 84.38
(C40), 84.23 (C10), 79.44 (CH2C^), 68.85 (C30), 63.86
(Ph3C), 60.84 (C50), 56.31 (^CCH2), 38.60 (C20), 17.38,
17.20 (3C), 17.07, 16.91 (2C), 16.82 (CH3), 12.76, 12.48,
12.05, 11.96 (SiC).
00
00
128.83, 128.74, 128.23, 128.06, 127.72 (C3a1 , C6b1 ,
00
00
C900, C1000, C12b ), 127.10, 126.95 (3C) (C200, C500, C8 ,
C1100), 124.24 (C4 ), 120.91 (2C), 120.79 (C600, C700, C12000),
120.07 (C100), 97.69 (C5), 88.95 (CH2C^C), 84.36 (C4 ),
84.18 (C10), 78.98 (CH2C^), 69.25 (C30), 68.86 (ArCH2),
60.81 (C50), 57.71 (CH2C^), 38.60 (C20), 17.33, 17.18
(3C), 17.07, 16.89 (2C), 16.81 (CH3), 12.76, 12.45, 12.02,
11.94 (SiC).
4.4.3. 30,50-O-(Tetraisopropyldisiloxane-1,3-diyl)-5-
(estron-3-yloxypropyn-1-yl)-20-deoxyuridine (18c). The
title compound was purified using a 0/20% gradient of
EtOAc in toluene (v/v); white amorphous solid (934 mg,
60%); Rf 0.25 (30% EtOAc in toluene (v/v)). ESI MS: m/zZ
799.8 [MCNa]C, calcd for [C42H60N2O8Si2CNa]C800.1.
ESI-TOF HRMS: m/zZ777.4019 [MCH]C, calcd for
[C42H60N2O8Si2CH]C777.3961. 1H NMR (DMSO-d6):
00 00
4.5. General procedure for the preparation of
5-alkynylated 20-deoxyuridines (19a–d)
To a solution of corresponding 5-alkynyl-30,50-O-(tetra-
isopropyldisiloxane-1,3-diyl)-20-deoxyuridine (1.00 mmol)
in THF (3 mL) in a teflon flask triethylamine trihydro-
fluoride (0.41 mL, 2.50 mmol) was added in one portion and
the mixture was left for 12 h at room temperature, then
diluted with hexane (25 mL). The upper layer was removed,
and the residue was washed with toluene/hexane mixture,
1:1 (25 mL (v/v)) by decantation, and the residue was
dissolved in chloroform (50 mL). The solution was washed
11.65 (s, 1H, NH); 7.88 (s, 1H, H-6); 7.18 (d, 1H, J1 ,2
Z
4
8.6 Hz, H-100); 6.75 (dd, 1H, J2 ,4 Z2.5 Hz, J1 ,2 Z8.6 Hz,
00 00
00 00
† Calculated value; the signal of solvent is also present in the region.