A. J. Moreno-Vargas et al. / Bioorg. Med. Chem. Lett. 12 (2002) 2335–2339
2339
Bulow, A.; Bols, M. J. Am. Chem. Soc. 2001, 123, 5116. (h)
Jensen, H.; Bols, M. J. Chem. Soc., Perkin Trans. 1 2001, 905.
6. (a) Fleet, G. W. J.; Nicholas, S. J.; Smith, P. W.; Evans,
S. V.; Fellows, L. E.; Nash, R. J. Tetrahedron Lett. 1985, 26,
3127. (b) Asano, N.; Oseki, K.; Kizu, H.; Matsui, K. J. Med.
Chem. 1994, 37, 3701. (c) Asano, N.; Nishida, M.; Miyauchi,
M.; Ikeda, K.; Yamamoto, M.; Kizu, H.; Kameda, Y.;
Watson, A. A.; Nash, R. J.; Fleet, G. W. J. Phytochemistry
2000, 53, 379.
7. Saotome, C.; Kanie, Y.; Kanie, O.; Wong, C.-H. Bioorg.
Med. Chem. 2000, 8, 2249 and references cited therein.
8. Popowycz, F.; Gerber-Lemaire, S.; Demange, R.; Rodrıguez-
Garcıa, E.; Carmona-Asenjo, A. T.; Robina, I.; Vogel, P.
Bioorg. Med. Chem. Lett. 2001, 11, 2489.
(2CH3CO), 163.1 (COOEt), 157.3 (CO of Cbz), 153.9, 149.3
(C-2, C-5), 136.8 (C-1 of Ph), 128.2–127.3 (5C, C-aromat of
0
Cbz), 113.9 (C-4), 108.6(C-3), 71.4 (C-3 ), 69.9 (C-40), 66.4
(CH2 of Cbz), 59.7 (CH2CH3), 55.3 (C-20), 49.2 (C-50), 20.2,
20.0 (2CH3CO), 14.1 (CH2CH3), 13.2 (CH3); CIMS m/z 474
[15%, (M+H)+]. Analysis calcd for C24H27NO9: C, 60.88; H,
5.75; N, 2.96. Found: C, 60.71; H, 5.99; N, 2.58.
14. Koole, L. H.; Moody, H. M.; Broeders, N. L. H. L.;
Quaedflieg, P. J. L. M.; Kuijpers, W. H. A.; van Genderen,
M. H. P.; Coenen, A. J. J. M.; van der Wal, S.; Buck, H. M. J.
Org. Chem. 1989, 54, 1657.
15. Data for 7: [a]D25 ꢀ13 (c 0.3, CH3OH). IR nmax 3404 (NH,
1
OH), 2974, 2932, 1661–1542 (CO), 1443, 1383, 1101 cmꢀ1. H
NMR (400 MHz, CD3OD, d ppm, J Hz) d 6.55 (s, 1H, H-3),
0
4.39–4.43 (m, 1H, H-40), 4.31 (d, 1H, J2 ,3 =3.9, H-2 ), 4.23 (t,
0
0
˜
9. Robina, I.; Moreno-Vargas, A. J.; Fernandez-Bolanos,
J. G.; Fuentes, J.; Demange, R.; Vogel, P. Bioorg. Med. Chem.
Lett. 2001, 11, 2555.
0
0
1H, J3 ,4 =3.9, H-3 ), 3.52 (bs, 4H, CH2 of RNHEt2), 3.26(dd,
0
1H, J4 ,5 a=7.5, J5 a,5 b=11.5, H-50a), 3.04 (dd, 1H,
0
0
0
0
10. Garcıa-Gonzalez, F. Adv. Carbohydr. Chem. 1956, 11, 97.
11. Corey, E. J.; Kim, C. U.; Takeda, M. Tetrahedron Lett.
1972, 4339.
J4 ,5 b=6.4, H-50b), 2.36(s, 3H, CH 3), 1.23 (d, 6H, CH3 of
RNHEt2); 13C NMR (100.5 MHz, CD3OD, d ppm) d 168.1
(CONEt2), 153.5 (C-5), 150.2 (C-2), 118.3 (C-4), 109.6(C-3),
73.5 (C-30), 73.3 (C-40), 60.2 (C-20), 51.0 (C-50), 44.6, 40.9 (CH2
of RNEt2), 14.6, 13.2 (CH3 of RNEt2), 12.8 (CH3); CIMS m/z
282 [15%, (M)+]. HREIMS m/z obsd 282.1584, calcd for
C14H22N2O4 282.1579.
0
0
12. Data for 15: [a]D25 ꢀ1 (c 1, CH2Cl2); H NMR (300 MHz,
1
DMSO-d6, 90 ꢁC, d ppm, J Hz) d 7.42–7.21 (m, 5H, H-aromat
of Cbz), 6.50 (s, 1H, H-3), 5.42–5.37 (m, 2H, H-30, H-40), 5.12,
2
5.01 (d, 1H each, JH,H=12.7, CH2 of Cbz), 4.84 (d, 1H,
0
16. Data for 8: [a]D25 ꢀ10 (c 0.3, CH3OH). IR nmax 3325 (NH,
3
0
J2 ,3 =3.3, H-2 ), 4.23 (q, 2H, JH,H=7.1, CH2CH3), 3.94 (dd,
0
1H, J4 ,5 a=5.6, J5 a,5 b=11.6, H-50a), 3.56(dd, 1H,
OH), 2930, 1634 (CO), 1588, 1402, 1101 cmꢀ1 1H NMR
.
0
0
0
0
J4 ,5 b=5.1, H-50b), 2.47 (s, 3H, CH3), 2.03, 2.02 (s, 3H each, 2
CH3CO), 1.23 (t, 3H, CH2CH3); 13C NMR (75.4 MHz,
DMSO-d6, 90 ꢁC, d ppm) d 168.9, 168.7 (2CH3CO), 162.3
(COOEt), 157.6(CO of Cbz), 153.4, 148.9 (C-2, C-5), 136.0
(C-1 of Ph), 127.7–126.7 (5C, C-aromat of Cbz), 113.6 (C-4),
107.8 (C-3), 73.9, 69.0 (C-30, C-40), 66.0 (CH2 of Cbz), 59.3
(CH2CH3), 57.4 (C-20), 47.8 (C-50), 19.7 (2CH3CO), 13.6
(CH2CH3), 12.8 (CH3); CIMS m/z 474 [30%, (M+H)+].
Analysis calcd for C24H27NO9: C, 60.88; H, 5.75; N, 2.96.
Found: C, 60.69; H, 6.11; N, 2.69.
(400 MHz, CD3OD, d ppm, J Hz) d 6.88 (s, 1H, H-3), 4.50–
0
0
0
4.45 (m, 2H, H-20, H-40), 4.29 (t, 1H, J3 ,4 =J2 ,3 =3.9, H-3 ),
0
0
0
0
3
4.18 (hept, 1H, JH,H=6.6, CH of Pri), 3.36–3.40 (m, 1H, H-
50a), 3.15 (dd, 1H, J4 ,5 b=6.4, J5 a,5 b=11.6, H-50b), 2.55 (s,
0
0
0
0
3H, CH3), 1.25 (d, 6H, JH,H=6.6, CH3 of Pri). 13C NMR
3
(100.5 MHz, CD3OD, d ppm) d 165.3 (CONHPri), 157.7 (C-5),
147.9 (C-2), 118.2 (C-4), 110.1 (C-3), 73.2 (C-30), 72.8 (C-40),
59.9 (C-20), 50.2 (C-50), 42.5 (CH of i-Pr), 22.6(CH of i-Pr),
3
13.5 (CH3); CIMS m/z 269 [8%, (M+H)+]. EIMS m/z 268
[8%, (M)+]. HREIMS m/z obsd 268.1429, calcd for
C13H20N2O4 268.1423.
17. See: (a) Picasso, S.; Chen, Y.; Vogel, P. Carbohydr. Lett.
1994, 1, 1. (b) Brandi, A.; Cicchi, S.; Cordero, F. M.; Fignoli,
B.; Goti, A.; Picasso, S.; Vogel, P. J. Org. Chem. 1995, 60,
6806, and refs 4d, 8 and 9.
18. Fleet, G. W. J.; Nicolas, S. J.; Smith, P. W.; Evans, S. V.;
Fellows, L. E.; Nash, R. J. Tetrahedron Lett. 1985, 26, 3127.
19. Saotome, C.; Kanie, Y.; Kanie, O.; Wong, C.-H. Bioorg.
Med. Chem. 2000, 8, 2249.
13. Data for 16: [a]2D5 +40 (c 0.6, CH2Cl2); 1H NMR
(300 MHz, DMSO-d6, 90 ꢁC, d ppm, J Hz) d 7.32–7.16(m, 5H,
0
H-aromat of Cbz), 6.30 (s, 1H, H-3), 5.44 (dd, 1H, J2 ,3 =7.2,
0
0
0
0
0
0
J3 ,4 =4.8, H-3 ), 5.39–5.34 (m, 1H, H-4 ), 5.14 (d, 1H, H-2 ),
2
5.07, 4.96(d, 1H each, JH,H=12.7, CH2 of Cbz), 4.20 (q, 2H,
3
0
0
0
0
JH,H=7.1, CH2CH3), 3.88 (dd, 1H, J4 ,5 a=5.8, J5 a,5 b=11.8,
H-50a), 3.54 (dd, 1H, J4 ,5 b=3.8, H-50b), 2.43 (s, 3H, CH3),
1.93, 1.84 (s, 3H each, 2 CH3CO), 1.25 (t, 3H, CH2CH3); 13C
NMR (75.4 MHz, DMSO-d6, 90 ꢁC, d ppm) d 169.3, 168.9
0
0