P. Kumar et al. / Tetrahedron Letters 43 (2002) 4427–4429
4429
References
(CDCl3): l 0.84–1.02 (m, 28H, 4×isopropyl H), 2.45 (br,
D2O exchangeable, 1H, OH), 4.05 (dd, 1H, J4%,5%=2.7 Hz,
Jgem=13.4 Hz, H-5%), 4.19 (d, J3%,2%=4.3 Hz, 1H, H-2%),
4.25 (dd, 1H, J3%,4%=9.2 Hz, J5%,4%=2.8 Hz, H-4%), 4.32 (d,
1H, Jgem=13.4 Hz, H-5%%), 4.43 (dd, 1H, J2%,3%=4.3 Hz,
J4%,3%=9.3 Hz, H-3%), 6.3 (s, 1H, H-1%), 7.09 (d, J5,4=1.1
Hz, 1H, H-4) and 7.74 (d, J4,5=1.1 Hz, 1H, H-5); 13C
NMR (CDCl3): l 12.60–13.46 (4 isopropyl CH), 16.87–
17.50 (8 isopropyl CH3), 59.86 (C-5%), 68.19 (C-4%), 76.97
(C-3%), 82.28 (C-2%), 92.33 (C-1%), 122.62 (C-5), 128.39
(C-4), 144.5 (C-2) ppm, Chem. Anal. Calcd: C, 49.256; H,
7.646; N, 8.616; found: C, 49.634; H, 7.39; N, 8.484%. 3:
1. Brown, J. M. Cancer Res. 1999, 59, 5863–5870.
2. Gray, L. H.; Conger, A. D.; Ebert, M.; Hornsey, S.;
Scott, O. C. Br. J. Radiol. 1953, 26, 638.
3. Crabtree, H. G.; Cramer, W. Proc. R. Soc. Ser. B 1933,
113, 238–250.
4. Stone, H. B.; Brown, M. J.; Philips, T. L.; Sutherland, R.
M. Radiat. Res. 1993, 136, 422–434.
5. Heimbrook, D. C.; Sartorelli, A. C. Molec. Pharmacol.
1986, 29, 168.
6. Grosher, D.; McEwan, A. J. B.; Parliament, M. B.;
Urtasun, R. C.; Golberg, L. E.; Hoskinson, M.; Mercer,
J. R.; Mannan, R. H.; Wiebe, L. I.; Chapman, J. D. J.
Nucl. Med. 1993, 34, 885.
7. Mannan, R. H.; Somayaji, V. V.; Lee, J.; Mercer, J. R.;
Chapman, J. D.; Wiebe, L. I. J. Nucl. Med. 1991, 32,
1764–1770.
8. Mannan, R. H.; Mercer, J. R.; Wiebe, L. I.; Kumar, P.;
Somayaji, V. V.; Chapman, J. D. J. Nucl. Biol. Med.
1992, 36, 60–67.
9. Parliament, M. B.; Chapman, J. D.; Urtasun, R. C.;
McEwan, A. J.; Goldberg, L.; Mercer, J. R.; Mannan, R.
H.; Wiebe, L. I. Br. J. Cancer 1991, 65, 90–95.
10. Urtasun, R. C.; Parliament, M. B.; McEwan, A. J.;
Mercer, J. R.; Mannan, R. H.; Wiebe, L. I.; Morin, C.;
Chapman, J. D. Br. J. Cancer 1996, 74, S209–S212.
11. Al-Arafaj, A.; Ryan, E. A.; Hutchinson, K.; Mannan, R.
H.; Mercer, J. R.; Wiebe, L. I.; McEwan, A. J. B. Eur. J.
Nucl. Med. 1994, 21, 1338–1342.
12. McEwan, A. J. B.; Skeith, K. J.; Mannan, R. H.; Davies,
N.; Jamali, F.; Schmidt, R.; Golberg, K.; Wiebe, L. I. J.
Nucl. Med. 1997, 38, 300 abstract.
13. Vinjamuri, S.; O’Driscol, K.; Maltby, P.; McEwan, A. J.;
Wiebe, L. I.; Critchley, M. Clin. Nucl. Med. 1999, 24,
891–892.
1-b-D-(3,5-O-Tetraisopropyldisilyloxy - 2 - O - trifluoro-
methanesulfonylribofuranosyl)-2-nitroimidazole: mp 50–
1
52°C. H NMR (CDCl3): l 0.88–1.05 (m, 28H, 4×isopro-
pyl H), 3.99 (dd, 1H, J4%,5%=2.4 Hz, Jgem=13.7 Hz,
H-5%), 4.17 (dd, 1H, J3%,4%=9.5 Hz, J5%,4%=2.4 Hz, H-4%),
4.28 (d, 1H, Jgem=13.7 Hz, H-5%%), 4.53 (dd, 1H, J2%,3%
=
3.8 Hz, J4%,3%=9.5 Hz, H-3%), 5.20 (d, J3%,2%=3.8 Hz, 1H,
H-2%), 6.48 (s, 1H, H-1%), 7.13 (d, J5,4=0.9 Hz, 1H, H-4)
and 7.81 (d, J4,5=0.9 Hz, 1H, H-5); 13C NMR (CDCl3):
l 12.87–13.40 (4 isopropyl CH), 16.56–17.50 (8 isopropyl
CH3), 59.02 (C-5%), 66.60 (C-4%), 82.30 (C-3%), 88.27 (C-2%),
89.58 (C-1%), 118.43 (CF3), 122.42 (C-5), 128.83 (C-4),
144.5 (C-2) ppm; Chem. Anal. Calcd: C, 40.698; H, 5.855;
N, 6.780; Found: C, 40.939; H, 6.235; N, 7.172. 4:
1-b-D-(3,5-O-Tetraisopropyldisilyloxy-2-deoxy-2-iodoara-
binofuranosyl)-2-nitroimidazole: mp 136–138°C. 1H
NMR (CDCl3): l 0.96–1.06 (m, 28H, 4×isopropyl H),
3.74 (ddd, 1H, J3%,4%=8.5 Hz, J5%,4%=2.8 Hz, J5%%,4%=1.8 Hz,
H-4%), 4.10 (dd, 1H, J4%,5%=2.8 Hz, Jgem=13.4 Hz, H-5%),
4.12 (d, 1H, Jgem=13.4 Hz, J4%,5%%=1.8 Hz, H-5%%), 4.53
(dd, 1H, J2%,3%=9.2 Hz, J4%,3%=8.5 Hz, H-3%), 4.65 (dd,
J3%,2%=9.2 Hz, J1%,2%=6.7 Hz, 1H, H-2%), 6.68 (d, J2%,1%=6.7
Hz 1H, H-1%), 7.09 (s, 1H, H-4) and 7.63 (s, 1H, H-5); 13
C
NMR (CDCl3): l 12.49–13.99 (4 isopropyl CH), 16.94–
17.31 (8 isopropyl CH3), 30.27 (C-2%), 60.14 (C-5%), 76.03
(C-4%), 84.04 (C-3%), 86.89 (C-1%), 121.72 (C-5), 128.22
(C-4), 145.5 (C-2) ppm, chem. Anal. Calcd: C, 40.198; H,
6.072; N, 7.031; found: C, 40.480; H, 6.900; N, 7.170. 5:
14. Wang, L.; Wiebe, L. I., unpublished.
15. Xu, L. M. Sc. Thesis, University of Alberta, 1988.
16. Kumar, P.; Wiebe, L. I.; Atrazheva, E.; Tandon, M.
Tetrahedron Lett. 2001, 42, 2077–2078.
17. Lee, H. C.; Kumar, P.; Wiebe, L. I.; McDonald, R.;
Mercer, J. R.; Ohkura, K.; Seki, K. Nucleosides Nucle-
otides 1999, 18, 1995–2016.
1-b-D-[2-Deoxy-2-iodoarabinofuranosyl]-2-nitroimida-
zole: mp 63–65°C. 1H NMR (CD3OD): 3.83–3.89 (m, 2H,
J3%,4%=7.3 Hz, J5%,4%=3.5 Hz, J5%%,4%=3.8 Hz, Jgem=13.2
Hz, H-4% and H-5%), 3.97 (dd, 1H, J4%,5%%=3.8 Hz, Jgem=
13.2 Hz, H-5), 4.52 (dd, 1H, J2%,3%=J4%,3%=7.3 Hz, H-3%),
4.78 (dd, J3%,2%=7.3 Hz, J1%,2%=6.4 Hz, 1H, H-2%), 6.69 (d,
J2%1%=6.4 Hz 1H, H-1%), 7.17 (d, 1H, J5,4=1.2 Hz, H-4)
and 8.10 (d, 1H, J4,5=1.2 Hz, H-5); 13C NMR (CD3OD):
l 30.39 (C-2%), 60.07 (C-5%), 78.00 (C-4%), 81.37 (C-3%),
84.44 (C-1%), 112.76 (C-5), 126.56 (C-4), 145.20 (C-2)
ppm; LR (ESI) MS m/z: 378 (M++Na), HR (ESI) MS
(M++Na, C8H10O5N3INa): Calc. mass 377.95629, exact
mass 377.95574.
18. Reist, E. J.; Benitez, A.; Goodman, L.; Baker, B. R.; Lee,
W. W. J. Org. Chem. 1962, 27, 3274–3279.
19. Cheriyan, U. O.; Ogilvie, K. K. Nucleosides Nucleotides
1982, 1, 233–237.
20. Kumar, P., unpublished data.
21. Jette, D. C.; Wiebe, L. I.; Flanagan, R. J.; Lee, J.;
Chapman, J. D. Radiation Res. 1986, 105, 169–179.
22. All new compounds gave satisfactory 1H NMR (300
MHz) spectroscopic and elemental analytical data.
Selected data: 2: 1-b-
D-(3,5-O-Tetraisopropyldisilyloxy-
ribofuranosyl)-2-nitroimidazole: mp 59–61°C. 1H NMR