3170
M. Popsavin et al. / Bioorg. Med. Chem. Lett. 13 (2003) 3167–3170
1
0
14. Kini, G. D.; Hennen, W. J. J. Org. Chem. 1986, 51, 4436.
15. Popsavin, M.; Popsavin, V.; Vukojevic, N.; Csanadi, J.;
Miljkovic, D. Carbohydr. Res. 1994, 260, 145.
10), 97.86 (d, J3 ,F=184.8 Hz, C-30), 125.62 (C-5), 150.88 (C-
4), 165.72 (C-2), 173.73 (C¼O); CI MS: m/z 263 (M++1).
19. Selected data for 14 (syrup): [a]D +24.93 (c 4.35 in
1
16. Popsavin, M.; Torovic, Lj.; Spaic, S.; Stankov, S.; Kapor,
A.; Tomic, Z.; Popsavin, V. Tetrahedron 2002, 58, 569.
17. Compound 6: mp 72.5–73 ꢀC (from CH2Cl2–pentane);
CHCl3); H NMR (CDCl3): d 2.04 (s, 3H, NHAc), 4.01–4.20
(m, 4H, 2ÂCH2-dioxolane), 4.31 (t, 1H, J1,2=J2,3=1.2 Hz, H-
2), 4.44–4.63 (m, 3H, J4,5=3.4 Hz, H-5 and 2ÂH-6), 4.88
(ddd, 1H, J3,4=0.6, J4,5=3.4, J4,NH=9.5 Hz, H-4), 5.31 (d,
1H, J1,2=1.2 Hz, H-1), 6.89(d, 1H, J4,NH=9.5 Hz, NH),
7.39–8.17 (m, 10H, 2ÂPh); 13C NMR (CDCl3): d 23.24
(MeCO), 54.85 (C-4), 62.92 (C-6), 65.63 and 65.67 (2ÂCH2-
dioxolane), 78.57 (C-3), 79.07 (C-5), 84.02 (C-2), 102.08 (C-1),
128.30, 128.45, 128.96, 129.72, 133.03 and 133.56 (2ÂPh),
165.38 and 166.22 (2ÂPhC¼O), 169.25 (MeCO); HR MS: m/z
478.1472 (M++Na); calcd for C24H25NO8Na: 478.1478.
20. Selected data for 3 (syrup): [a]D À3.93 (c 1.3 in MeOH);
1H NMR (methanol-d4): d 1.97 (s, 3H, MeCO), 3.68 (dd, 1H,
1
[a]D À22.19( c 2.3 in CHCl3); H NMR (CDCl3): d 3.95–4.09
(m, 4H, 2ÂCH2-dioxolane), 4.14 (dd, 1H, J1,2=5.2, J2,3=3
Hz, H-2); 4.49(dddd, 1H, J4,5=2.7, J5,6a=5.8, J5,6b=5.6,
J5,F=28.9Hz, H-5), 4.64–4.74 (m, 2H, J6a,6b=11.7, J5,6a=5.8,
J5,6b=5.6, J6a,F=1 Hz, 2ÂH-6), 5.16 (d, 1H, J1,2=5.2 Hz, H-
1), 5.19(ddd, 1H, J3,4=0.5, J4,5=2.7, J4,F=50.4 Hz, H-4),
5.69(ddd, 1H, J3,4=0.5, J3,F=16.2, J2,3=3 Hz, H-3), 7.43–
8.15 (m, 10H, 2ÂPh); 13C NMR (CDCl3): d 61.53 (d,
3J6,F=10.6 Hz, C-6), 65.42 and 65.52 (2ÂCH2-dioxolane),
2
2
77.39(d, J3,F=31.4 Hz, C-3), 79.28 (d, J5,F=19.5 Hz, C-5),
1
84.22 (C-2), 94.64 (d, J4,F=188.5 Hz, C-4), 102.27 (C-1),
J5 a,5 b=12.3, J4 ,5 a=4.6 Hz, H-50a), 3.79(dd, 1H,
0 0 0 0
0
0
0
0
0
0
128.33, 128.51, 128.84, 129.56, 129.72, 129.77, 133.16 and
133.66 (2ÂPh), 164.96 and 166.14 (2ÂC¼O); CI MS: m/z 417
(M++1). Anal. found: C, 63.21; H, 5.05; calcd for
C22H21FO7: C, 63.46; H, 5.08.
J5 a,5 b=12.3, J4 ,5 b=3.5 Hz, H-50b), 4.36 (t, 1H, J1 ,2 =5.8,
0
0
0
0
0
0
0
0
J2 ,3 =5.7 Hz, H-2 ), 4.40 (ddd, 1H, J4 ,5 a=4.6, J4 ,5 b=3.5,
J3 ,4 =6.6 Hz, H-4 ), 4.47 (dd, 1H, J2 ,3 =5.7, J3 ,4 =6.6 Hz,
0
0
0
0
0
0
0
H-30), 4.98 (d, 1H, J1 ,2 =5.8 Hz, H-1 ), 8.23 (s, 1H, H-5); 13C
NMR (methanol-d4): d 22.52 (MeCO), 59.96 (C-30), 61.88 (C-
50), 81.22 (C-40), 81.81 (C-20), 83.83 (C-10), 125.86 (C-5), 150.80
(C-4), 165.66 (C-2), 172.60 (CONH2), 173.75 (MeCO). Anal.
Found: C, 44.02; H, 5.18; N, 13.67; S, 10.43; calcd for
C11H15N3O5S: C, 43.85; H, 5.02; N, 13.95; S, 10.64.
0
0
18. Selected data for 2 (syrup): [a]D À35.91 (c 1.04 in MeOH);
1H NMR (methanol-d4): d 3.91 (pseudo d, 2H, J4 ,5 =6.4 Hz,
0
0
2ÂH-50), 4.38 (dtd, 1H, J4 ,F=30.7, J3 ,4 =2.4, J4 ,5 =6.4 Hz,
0
0
0
0
0
H-40), 4.57 (ddd, 1H, J1 ,2 =1.2, J2 ,3 =0.6, J2 ,F=13.9Hz, H-
0
0
0
0
0
20), 4.97 (ddd, 1H, J2 ,3 =0.6, J3 ,4 =2.4, J3 ,F=50.7 Hz, H-30),
0
0
0
0
0
5.13 (d, 1H, J1 ,2 Hz,=1.2, H-10), 8.15 (s, 1H, H-5); 13C NMR
21. Scudiero, D. A.; Shoemaker, R. H.; Paull, K. D.; Monks,
A.; Tierney, S.; Nofziger, T. H.; Currens, M. J.; Seniff, D.;
Boyd, M. R. Cancer Res. 1988, 48, 4827.
0
0
(methanol-d4): d 60.21 (d, J5 ,F=10.7 Hz, C-50), 81.72 (d,
3
0
J4 ,F=27 Hz, C-40), 84.04 (d, J2 ,F=19.4 Hz, C-20), 86.56 (C-
2
2
0
0