R. Namme et al. / Tetrahedron 62 (2006) 9183–9192
9191
103.9, 79.7, 75.6, 74.2, 72.5, 71.4, 70.9, 69.5, 68.1, 64.3,
63.1, 21.9.
4.3.16. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/3)-D-man-
nono-1,5-lactone (15cc). Colorless amorphous solid; [a]D28
+76.4 (c 0.99, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.61 (dd, J¼3.3 Hz, 1H, H-2), 4.18 (dd, J¼3.3, 0.6 Hz,
1H, H-3), 4.15 (ddd, J¼2.5, 5.0, 9.9 Hz, 1H, H-60), 4.03
(ddd, J¼2.5, 5.2, 8.0 Hz, 1H, H-5), 3.82 (m, 1H, H-4),
3.75 (dd, J¼2.5, 12.7 Hz, 1H, H-6), 3.72 (dd, J¼3.3,
9.6 Hz, 1H, H-40), 3.67 (dd, J¼2.5, 11.8 Hz, 1H, H-70),
3.62 (dd, J¼5.0, 12.7 Hz, 1H, H-6), 3.60 (dd, J¼5.2,
11.8 Hz, 1H, H-70), 3.48 (d, J¼3.3 Hz, 1H, H-30), 3.46 (dd,
J¼9.6, 9.9 Hz, 1H, H-50), 1.41 (s, 3H, H-10); 13C NMR
(150 MHz, CD3OD): d 175.0, 103.3, 82.6, 76.5, 75.2, 74.4,
72.4, 70.2, 68.8, 68.0, 62.9, 62.4, 22.4.
4.3.10. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/3)-D-glu-
cono-1,5-lactone (15aa). Colorless amorphous solid; [a]D28
+87.7 (c 1.02, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.57 (dd, J¼6.9, 6.9 Hz, 1H, H-3), 4.49 (d, J¼6.9 Hz,
1H, H-2), 4.43 (dd, J¼6.9, 8.0 Hz, 1H, H-4), 3.89 (m, 1H,
H-5), 3.72–3.66 (m, 3H, H-6, H-50, H-60), 3.62–3.53 (m,
3H, H-6, H-40, H-70), 3.29 (m, 1H, H-70), 3.14 (d,
J¼9.4 Hz, 1H, H-30), 1.46 (s, 3H, H-10); 13C NMR
(150 MHz, CD3OD): d 176.1, 102.9, 78.8, 77.7, 76.1, 75.3,
74.5, 72.1, 71.4, 71.2, 64.0, 62.2, 21.9.
4.3.11. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/3)-D-galac-
tono-1,5-lactone (15ab). Colorless amorphous solid; [a]D25
+44.4 (c 1.02, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.52–4.48 (m, 2H), 4.28 (m, 1H), 3.80 (m, 1H), 3.72–
3.69 (m, 2H), 3.60–3.50 (m, 4H), 3.17 (dd, J¼9.4, 9.6 Hz,
1H), 3.10 (dd, J¼9.6 Hz, 1H, H-2), 1.45 (s, 3H, H-10); 13C
NMR (150 MHz, CD3OD): d 175.9, 102.8, 80.1, 78.2,
76.0, 75.1, 75.1, 74.6, 72.1, 70.5, 63.7, 62.7, 22.1.
4.3.17. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/4)-D-glu-
cono-1,5-lactone (20aa). Colorless amorphous solid; [a]D25
+93.0 (c 0.96, CH3OH); H NMR (600 MHz, D2O): d 4.65
(m, 1H), 4.41 (m, 1H), 4.15 (m, 1H), 3.74–3.62 (m, 5H),
3.57–3.51 (m, 2H), 3.19 (m, 1H), 3.12 (m, 1H), 1.28
(s, 3H, H-10); 13C NMR (150 MHz, D2O): d 178.0,
102.9, 80.1, 77.0, 74.1, 74.0, 73.8, 73.7, 73.4, 70.7, 62.3,
61.4, 21.4.
1
4.3.12. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/3)-D-glu-
cono-1,5-lactone (15ba). Colorless amorphous solid; 1H
NMR (600 MHz, CD3OD): d 4.58 (dd, J¼6.9, 7.2 Hz, 1H,
H-3), 4.51 (d, J¼7.2 Hz, 1H, H-2), 4.43 (dd, J¼6.9,
7.7 Hz, 1H, H-4), 3.95 (m, 1H), 3.87 (m, 1H, H-5), 3.82
(m, 1H), 3.68–3.65 (m, 2H), 3.63–3.52 (m, 4H), 1.46 (s,
3H, H-10); 13C NMR (150 MHz, CD3OD): d 176.1, 103.2,
78.7, 76.0, 74.4, 73.1, 72.1, 71.9, 71.6, 71.0, 64.0, 62.6, 21.9.
4.3.18. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/4)-D-galac-
tono-1,5-lactone (20ab). Colorless amorphous solid; [a]D25
+135.2 (c 0.6, H2O); H NMR (600 MHz, D2O): d 4.46
(m, 2H), 4.40 (m, 1H), 4.04 (m, 1H), 3.84 (m, 1H), 3.70
(m, 1H), 3.66–3.58 (m, 3H), 3.54 (m, 1H), 3.24 (m, 1H),
3.19 (m, 1H), 1.28 (s, 3H, H-10); 13C NMR (150 MHz,
D2O): d 177.0, 102.0, 81.0, 77.0, 74.6, 73.6, 73.3, 73.3,
71.4, 70.3, 61.0, 60.5, 21.4.
1
4.3.13. 1-Deoxy-D-galacto-hept-2-ulosyl-(2/3)-D-galac-
tono-1,5-lactone (15bb). Colorless amorphous solid; 1H
NMR (600 MHz, CD3OD): d 4.53 (d, J¼8.0 Hz, 1H, H-2),
4.48 (dd, J¼8.0, 8.0 Hz, 1H), 4.27 (dd, J¼2.5, 8.0 Hz, 1H,
H-3), 3.93 (m, 1H), 3.79 (m, 1H, H-4), 3.71–3.69 (m, 2H),
3.66 (dd, J¼3.0, 10.2 Hz, 1H, H-40), 3.60–3.54 (m, 3H),
3.50 (dd, J¼10.2 Hz, 1H, H-30), 1.48 (s, 3H, H-10); 13C
NMR (150 MHz, CD3OD): d 176.0, 103.1, 80.0, 76.0,
74.9, 74.5, 73.7, 71.7, 71.4, 70.6, 63.7, 63.1, 21.9.
4.3.19. 1-Deoxy-a-D-gluco-hept-2-ulosyl-(2/4)-D-man-
nono-1,5-lactone (20ac). Colorless amorphous solid; [a]D25
+135.2 (c 0.6, H2O); 1H NMR (600 MHz, D2O): d 4.65 (d,
J¼2.8 Hz, 1H, H-2), 4.29 (m, 1H, H-5), 4.03 (m, 1H, H-
3), 3.93 (m, 1H, H-4), 3.71 (dd, J¼2.2, 12.4 Hz, 1H, H-70),
3.63–3.59 (m, 2H, H-6, H-6), 3.55 (dd, J¼5.0, 12.4 Hz,
1H, H-70), 3.46 (dd, J¼9.4, 9.6 Hz, 1H), 3.37 (ddd, J¼2.2,
5.0, 9.9 Hz, 1H, H-60), 3.21 (dd, J¼9.6, 9.6 Hz, 1H), 3.10
(d, J¼9.9 Hz, 1H, H-30), 1.37 (s, 3H, H-10); 13C NMR
(150 MHz, D2O): d 175.2, 102.7, 81.3, 76.4, 73.9, 73.8,
73.4, 70.3, 70.1, 68.9, 61.9, 61.1, 22.1.
4.3.14. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/3)-D-glu-
cono-1,5-lactone (15ca). Colorless amorphous solid; [a]D26
+59.6 (c 0.69, CH3OH); 1H NMR (600 MHz, CD3OD):
d 4.63 (d, J¼7.2 Hz, 1H, H-2), 4.59 (dd, J¼6.9, 7.2 Hz,
1H, H-3), 4.53 (dd, J¼4.4, 6.9 Hz, 1H, H-4), 3.87 (m, 1H),
3.78 (dd, J¼3.3, 9.6 Hz, 1H, H-40), 3.72–3.69 (m, 2H),
3.64–3.58 (m, 3H), 3.59 (d, J¼3.3 Hz, 1H, H-30), 3.52 (dd,
J¼9.6, 9.6 Hz, 1H, H-50), 1.42 (s, 3H, H-10); 13C NMR
(150 MHz, CD3OD): d 176.8, 104.1, 80.1, 76.2, 75.2, 74.7,
73.0, 72.7, 72.3, 67.9, 64.2, 62.6, 20.8.
4.3.20. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/4)-D-glu-
cono-1,5-lactone (20ba). Colorless amorphous solid; 1H
NMR (600 MHz, CD3OD): d 4.62 (dd, J¼4.9, 7.1 Hz, 1H,
H-4), 4.24 (dd, J¼3.6, 4.9 Hz, 1H, H-3), 4.21 (d, J¼3.6 Hz,
1H, H-2), 4.07 (ddd, J¼1.1, 4.1, 8.2 Hz, 1H, H-60), 4.05
(ddd, J¼7.1, 3.3, 3.6 Hz, 1H, H-5), 3.88 (dd, J¼3.3,
12.7 Hz, 1H, H-6), 3.76 (dd, J¼3.3, 1.1 Hz, 1H, H-50), 3.67–
3.64 (m, 3H, H-6, H-40, H-70), 3.56 (dd, J¼4.1, 11.3 Hz, 1H,
H-70), 3.48 (d, J¼9.9 Hz, 1H, H-30), 1.44 (s, 3H, H-10).
4.3.15. 1-Deoxy-a-D-manno-hept-2-ulosyl-(2/3)-D-gal-
actono-1,5-lactone (15cb). Colorless amorphous solid;
[a]2D5 +7.39 (c 0.57, CH3OH); 1H NMR (600 MHz,
CD3OD): d 4.61 (dd, J¼7.7, 8.0 Hz, 1H, H-50), 4.51 (d,
J¼8.0 Hz, 1H, H-2), 4.23 (dd, J¼1.7, 8.0 Hz, 1H, H-3),
3.80 (dd, J¼2.2, 11.3 Hz, 1H, H-6), 3.75 (dd, J¼3.3,
9.6 Hz, 1H, H-70), 3.67 (dd, J¼2.2, 7.7 Hz, 1H, H-40), 3.67
(m, 1H, H-5), 3.57–3.52 (m, 4H, H-4, H-6, H-30, H-60),
3.47 (dd, J¼9.6, 9.9 Hz, 1H, H-70), 1.44 (s, 3H, H-10); 13C
NMR (150 MHz, CD3OD): d 175.9, 104.0, 80.0, 79.6,
75.9, 75.6, 75.0, 74.7, 72.6, 69.7, 68.0, 63.5, 20.8.
4.3.21. 1-Deoxy-a-D-galacto-hept-2-ulosyl-(2/4)-D-gal-
actono-1,5-lactone (20bb). Colorless amorphous solid;
1H NMR (600 MHz, CD3OD): d 4.99 (dd, J¼2.2, 5.8 Hz,
1H, H-4), 4.33 (dd, J¼5.8, 6.3 Hz, 1H, H-3), 4.17 (d,
J¼6.3 Hz, 1H, H-2), 3.96–3.90 (m, 2H), 3.78–3.76 (m,
2H), 3.62–3.55 (m, 4H), 3.46 (d, J¼9.9 Hz, 1H), 1.46
(s, 3H, H-10); 13C NMR (150 MHz, CD3OD): d 177.1,
102.9, 83.0, 76.3, 75.4, 75.3, 73.4, 73.2, 71.3, 71.1, 62.7,
61.5, 21.6.