810
Krist et al.:
twice with toluen e. Th e residue obtain ed after evaporation was ch rom atograph ed
(CH2Cl2–EtOAc, 2:3) to afford 12 or 13 (167 m g, 85%), both in form of yellowish solid.
Compound 12. 1H NMR (CDCl3): 2.020 (3 H, s, CH3CO-6); 2.045 (3 H, s, CH3CO-3); 2.062
(3 H, s, CH3CO-4); 2.101 (3 H, s, CH3CONH-2); 4.009 (1 H, ddd, J = 2.8, 5.6, 10.2, H-5);
4.028 (1 H, dd, J = 2.8, 12.4, H-6a); 4.260 (1 H, dd, J = 5.6, 12.4, H-6b); 4.821 (1 H, ddd, J =
1.7, 4.8, 8.4, H-2); 5.201 (1 H, dd, J = 10.2, 10.2, H-4); 5.554 (1 H, dd, J = 4.8, 10.2, H-3);
5.626 (1 H, d, J = 1.7, H-1); 5.942 (1 H, d, J = 8.4, CH3CONH-2); 7.202 (2 H, m , H-ortho);
8.222 (2 H, m , H-meta). 13C NMR (CDCl3): 20.57 (q, CH3CO-4), 20.60 (q, CH3CO-6), 20.66
(q, CH3CO-3), 23.26 (q, CH3CONH-2), 50.42 (d, C-2), 61.97 (t, C-6), 65.63 (d, C-4), 68.38 (d,
C-3), 69.35 (d, C-5), 96.94 (d, C-1), 116.24 (d, 2 × C-ortho), 125.80 (d, 2 × C-meta), 143.21 (s,
C-para), 160.24 (s, C-ipso), 169.66 (s, CH3CO-3), 169.81 (s, CH3CO-4), 170.22 (s, CH3CO-6),
170.33 (s, CH3CONH-2).
Compound 13. 1H NMR (CDCl3): 2.043 (3 H, s, CH3CO-6); 2.070 (3 H, s, CH3CO-3); 2.101
(3 H, s, CH3CO-4); 2.116 (3 H, s, CH3CO-2); 3.924 (1 H, ddd, J = 3.4, 6.5, 8.3, H-5); 4.189
(1 H, dd, J = 3.4, 12.2, H-6a); 4.289 (1 H, dd, J = 6.5, 12.2, H-6b); 4.990 (1 H, ddd, J = 2.1,
3.9, 9.0, H-2); 5.107 (1 H, dd, J = 3.9, 9.0, H-3); 5.162 (1 H, dd, J = 8.3, 9.0, H-4); 5.416 (1 H,
d, J = 2.1, H-1); 5.945 (1 H, d, J = 9.0, CH3CONH-2); 7.069 (2 H, m , H-ortho); 8.206 (2 H, m ,
H-meta). 13C NMR (CDCl3): 20.59 (q, CH3CO-6), 20.65 (q, CH3CO-4), 20.70 (q, CH3CO-3),
23.34 (q, CH3CO-2), 49.39 (d, C-2), 62.33 (t, C-6), 65.80 (d, C-4), 70.72 (d, C-3), 73.03 (d,
C-5), 96.22 (d, C-1), 116.49 (d, 2 × C-ortho), 125.75 (d, 2 × C-meta), 143.24 (s, C-para),
160.90 (s, C-ipso), 169.58 (s, CH3CO-4), 170.11 (s, CH3CO-3), 170.23 (s, CH3CO-6), 170.60
(s, CH3CO-2). MALDI MS, m/z: 491.2 [M + Na]+.
4-Nitroph en yl 2-Acetam ido-2-deoxy-α-D-m an n opyran oside (14)
To a solution of 12 (50 m g, 0.11 m m ol) in m eth an ol (5 m l), sodium m eth oxide (2 M in
m eth an ol) was added to reach pH 10, an d th e m ixture was stirred for 2 h un til th e com plete
con version of 12 (TLC; CH2Cl2–EtOAc, 1:4). Th e reaction m ixture was n eutralized with
Dowex 50W-X2 (H form ), filtered an d con cen trated to give 14 (35 m g, 96%) as a wh ite
solid. 1H NMR (D2O): 1.880 (3 H, s, CH3CONH-2); 3.445 (1 H, dd, J = 2.4, 4.6, 10.0, H-5);
3.521 (1 H, dd, J = 9.6, 9.8, H-4); 3.533 (1 H, dd, J = 2.4, 12.4, H-6a); 3.587 (1 H, dd, J = 4.6,
12.4, H-6b); 4.053 (1 H, dd, J = 4.8, 9.6, H-3); 4.386 (1 H, dd, J = 1.6, 4.8, H-2); 5.487 (1 H,
d, J = 1.6, H-1); 5.942 (1 H, d, J = 8.4, CH3CONH-2); 7.034 (2 H, m , H-ortho); 8.013 (2 H, m ,
H-meta). 13C NMR (D2O): 22.07 (q, CH3CONH-2), 52.40 (d, C-2), 60.25 (t, C-6), 66.55 (d,
C-4), 68.93 (d, C-3), 73.52 (d, C-5), 96.92 (d, C-1), 116.76 (d, 2 × C-ortho), 126.16 (d, 2 ×
C-meta), 142.48 (s, C-para), 160.84 (s, C-ipso), 175.06 (s, CH3CONH-2). [α ]2D2 +53 (c 0.69
g/m ol, water). For C14H18N2O8 (342.3) calculated: 49.12% C, 5.30% H, 8.18% N; foun d:
49.33% C, 5.45% H, 8.21% N.
4-Nitroph en yl 2-Acetam ido-2-deoxy-β-D-m an n opyran oside (15)
Com poun d 15 was prepared from 13 (50 m g, 0.11 m m ol), usin g an an alogous procedure for
com poun d 14, in th e yield of 35 m g (96%) as a wh ite solid. 1H NMR (D2O): 1.925 (3 H, s,
CH3CONH-2); 3.44 (1 H, m , H-5); 3.45 (1 H, m , H-4); 3.646 (1 H, dd, J = 4.6, 12.4, H-6a);
3.737 (1 H, dd, J = 1.8, 12.4, H-6b); 3.74 (1 H, m , H-3); 4.51 (1 H, m , H-2); 5.378 (d, J = 1.7,
H-1); 6.939 (2 H, m , H-ortho); 8.006 (2 H, m , H-meta). 13C NMR (D2O): 22.32 (q, CH3CO-2),
53.14 (d, C-2), 60.58 (t, C-6), 66.83 (d, C-4), 71.93 (d, C-3), 77.00 (d, C-5), 96.74 (d, C-1),
116.77 (d, 2 × C-ortho), 126.38 (d, 2 × C-meta), 142.86 (s, C-para), 161.53 (s, C-ipso), 175.96
Collect. Czech. Chem. Commun. (Vol. 68) (2003)