R. C. Larock et al. / Tetrahedron 61 (2005) 11427–11439
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were obtained as a light yellow waxy, inseparable 50:50
mixture of diastereomers in 0a 70% combined yield from
the coupling of (C)-5-iodo-2 -deoxyuridine, 5 equiv of 1,4-
cyclohexadiene and 2 equiv of morpholine using the
3174, 2967, 2943, 2863, 1740, 1709, 1677, 1459, 1245,
1124 cmK1; HRMS for C24H35N3O8: calcd 493.2424, found
493.2429. This compound was not stable enough to measure
its melting point.
1
standard procedure: H NMR (CD3OD) d 1.85 (m, 1H),
2.22–2.42 (m, 4H), 3.00 (m, 1H), 3.10–3.21 (m, 4H), 3.56
(m, 1H), 3.74 (dd, JZ12.0, 3.3 Hz, 1H), 3.80 (dd, JZ12.0,
2.7 Hz, 1H), 3.85 (t, JZ4.8 Hz, 4H), 3.93 (m, 1H), 4.41 (m,
1H), 5.88 (m, 1H), 6.25 (m, 1H), 6.30 (t, JZ6.6 Hz, 1H),
6.31 (t, JZ6.6 Hz, 1H), 7.86 (s, 1H), 7.89 (s, 1H), the OH
and NH peaks overlapped with the water peak at d 4.93; 13C
NMR (CD3OD) d 27.7, 28.0, 29.5, 29.6, 40.1, 48.7, 49.7,
58.2, 61.3, 61.5, 66.7, 70.9, 71.0, 85.0, 85.2, 87.5, 87.6,
117.6, 117.8, 126.3, 126.4, 130.3, 135.8, 135.9, 151.3,
164.9, 165.0; IR (neat) 3402, 3196, 2928, 2855, 1708, 1666,
1465, 1276, 1110 cmK1; HRMS for C19H27N3O6: calcd
393.1899, found 393.1890.
4.3.10. Compounds 20a and 20b. Compounds 20a and 20b
were obtained as a yellow wax and an inseparable 67:33
mixture of isomers in a 51%0 combined yield from the
coupling of diacetyl 5-iodo-2 -deoxyuridine, 5 equiv of
1,9-decadiene and 2 equiv of morpholine using the standard
1
procedure: H NMR (CD3COCD3) d 1.15 (d, JZ6.9 Hz,
3H, 20b), 1.23–1.70 (m, 10H), 1.99–2.07 (m, 4H), 2.08 (s,
3H), 2.11 (s, 3H), 2.28–2.51 (br m, 7H), 2.90 (d, JZ6.3 Hz,
1H), 3.59 (t, JZ4.8 Hz, 4H), 4.22–2.31 (m, 2H), 4.37 (m,
1H), 5.28 (m, 1H), 5.43 (m, 1H), 5.60 (m, 1H), 6.30 (dd, JZ
8.4, 6.0 Hz, 1H), 7.38 (s, 1H, 20b), 7.49 (s, 1H), 9.69 (br s,
1H); 13C NMR (CD3COCD3) d 19.0, 19.3, 20.1, 20.13, 20.2,
26.9, 27.1, 31.4, 32.2, 35.3, 36.5, 36.6, 53.4, 53.6, 61.0,
63.9, 64.0, 66.5, 66.6, 74.5, 74.6, 82.1, 82.2, 84.8, 85.2,
114.9, 119.4, 126.5, 134.2, 134.5, 135.4, 150.1, 150.4,
162.8, 163.1, 169.9, 170.0; IR (neat) 3188, 2956, 2928,
2860, 1741, 1698, 1680, 1455, 1234, 1109 cmK1; HRMS
for C27H41N3O8: calcd 535.2894, found 535.2900.
4.3.7. Compound 13. Compound 13 was obtained as a
yellow wax in a 44% yield from the coupling of
5-iodouridine, 5 equiv of 1,5-hexadiene and 2 equiv of
morpholine using the standard procedure: 1H NMR
(CD3OD) d 1.57 (quintet, JZ7.2 Hz, 2H), 2.06 (q, JZ
6.6 Hz, 2H), 2.27 (t, JZ7.2 Hz, 2H), 2.67 (br s, 4H), 3.19
(m, 2H), 3.71–3.79 (m, 6H), 3.99 (m, 1H), 4.15–4.21 (m,
2H), 5.50 (dt, JZ15.3, 6.9 Hz, 1H), 5.77 (dt, JZ15.3,
6.6 Hz, 1H), 5.89 (d, JZ4.2 Hz, 1H), 7.86 (s, 1H), the OH
and NH peaks overlapped with the water peak at d 4.96; 13C
NMR (CD3OD) d 27.1, 28.5, 32.6, 53.7, 61.3, 62.2, 66.7,
71.4, 75.6, 86.5, 90.1, 115.4, 124.1, 138.5, 139.1, 152.5,
165.8; IR (neat) 3325, 3180, 2933, 2866, 2479, 1703, 1668,
1457, 1271, 1107 cmK1; HRMS for C19H29N3O7: calcd
411.2006, found 411.2003.
4.3.8. Compound 14. Compound 14 was obtained as a
yellow wax in a 53% yield from the coupling of (C)-5-iodo-
20-deoxyuridine, 5 equiv of 1,5-hexadiene and 2 equiv of
piperidine using the standard procedure: 1H NMR (CD3OD)
d 1.73–1.77 (m, 2H), 1.80–2.11 (m, 6H), 2.20 (q, JZ6.9 Hz,
2H), 2.29 (m, 2H), 2.35–2.40 (m, 6H), 3.18 (d, JZ6.0 Hz,
2H), 3.61–3.67 (m, 3H), 3.96 (dd, JZ6.3, 3.0 Hz, 1H), 4.46
(m, 1H), 5.66 (dt, JZ15.3, 7.2 Hz, 1H), 6.09 (dt, JZ15.3,
7.2 Hz, 1H), 6.33 (t, JZ6.9 Hz, 1H), 7.92 (s, 1H), the OH
and NH peaks overlapped with the water peak at d 4.94; 13C
NMR (CD3OD) d 23.4, 24.7, 25.8, 27.4, 31.3, 40.0, 53.5,
60.6, 61.4, 70.9, 85.0, 87.5, 114.1, 124.6, 136.8, 137.1,
151.0, 162.5; IR (neat) 3400, 3042, 2933, 2500, 1702, 1665,
1446, 1277, 1098 cmK1; HRMS for C20H29N3O5: calcd
393.2834, found 393.2838.
4.3.11. Compounds 21a and 21b. Compounds 21a and 21b
were obtained as a yellow wax as an inseparable 66:34
mixture of isomers in a 34%0 combined yield from the
coupling of diacetyl 5-iodo-2 -deoxyuridine, 5 equiv of
1,13-tridecadiene and 2 equiv of morpholine using the
4.3.9. Compound 18. Compound 18 was obtained as a light
yellow solid in a 61% yield from the coupling of diacetyl
5-iodo-20-deoxyuridine, 5 equiv of 2-methyl-1,5-hexadiene
and 2 equiv of morpholine using the standard procedure: 1H
NMR (CDCl3) d 1.56 (quintet, JZ7.5 Hz, 2H), 1.63 (s, 3H),
2.07 (q, JZ7.5 Hz, 2H), 2.119 (s, 3H), 2.123 (s, 3H), 2.18
(m, 1H), 2.33 (m, 6H), 2.48 (m, 1H), 2.82 (s, 2H), 3.70 (t,
JZ7.5 Hz, 4H), 4.25 (m, 1H), 4.37 (m, 2H), 5.21 (dt, JZ
6.6, 1.8 Hz, 1H), 5.31 (t, JZ7.5 Hz, 1H), 6.33 (dd, JZ8.7,
5.7 Hz, 1H), 7.23 (s, 1H), 9.53 (br s, 1H); 13C NMR (CDCl3)
d 25.10, 20.82, 20.92, 27.00, 27.48, 28.52, 37.55, 53.53,
63.91, 67.08, 67.73, 74.16, 82.14, 84.93, 115.82, 127.40,
132.66, 134.30, 150.25, 163.10, 170.13, 170.43; IR (neat)
1
standard procedure: H NMR (CD3COCD3) d 1.10 (d, JZ
6.9 Hz, 3H, 21b), 1.15–1.49 (m, 17H), 1.99–2.05 (m, 4H),
2.07 (s, 3H), 2.09 (s, 3H), 2.69–2.88 (br m, 7H), 2.87 (d, JZ
6.3 Hz), 3.58 (t, JZ4.8 Hz, 4H), 4.25–4.37 (m, 3H), 5.25
(m, 1H), 5.47 (m, 1H), 5.62 (m, 1H), 6.30 (dd, JZ8.4,
6.0 Hz, 1H), 7.37 (s, 1H, 21b), 7.48 (s, 1H), 9.69 (br s, 1H);
13C NMR (CD3COCD3) d 20.1, 20.8, 20.9, 27.7, 33.0, 36.1,
37.3, 37.4, 54.2, 61.8, 64.6, 64.7, 67.3, 69.2, 69.3, 75.3,
75.4, 115.7, 120.2, 127.3, 134.9, 135.3, 136.1, 150.9, 151.1,
163.5, 163.8, 170.7, 170.8; IR (neat) 3177, 2950, 2913,
2830, 1723, 1698, 1676, 1434, 1230, 1098 cmK1; HRMS
for C31H49N3O8: calcd 591.3520, found 591.3515.