G.-B. Zhou et al. / Tetrahedron 61 (2005) 5671–5677
5675
68.2, 62.1, 38.9–39.1, 27.2–27.4; IR (KBr, cmK1): n 2969,
1733, 1639, 1614, 1582, 1481, 1397, 1281, 1141, 941, 754.
Anal. Calcd for C33H48FNO9: C, 63.75; H, 7.78; N, 2.25.
Found: C, 63.71; H, 7.76; N, 2.28.
was recrystallized from heptane to give N-(2,3,4,6-tetra-O-
pivaloylated-D-glucopyranosyl)-amino nitriles 3.
4.3.1. N-(2,3,4,6-Tetra-O-pivaloylated-D-glucopyrano-
syl)phenylglycinonitrile (3a). Mp 152–155 8C; yield
1
4.2.8. 4-Nitro-N-(2,3,4,6-tetra-O-pivaloylated-D-gluco-
pyranosyl)benzylideneamine (2h). Mp 180–185 8C; yield
95%; m/z (ESI): 649.2 [MCH]C; 1H NMR (CDCl3): d 8.50
(s, 1H), 8.26 (d, JZ8.4 Hz, 2H), 7.85 (d, JZ8.4 Hz, 2H),
5.50 (t, JZ9.5 Hz, 1H), 5.23 (t, JZ9.7 Hz, 1H), 5.00 (t, JZ
9.2 Hz, 1H), 4.96 (t, JZ9.2 Hz, 1H), 4.31 (d, JZ12 Hz,
1H), 4.18 (q, JZ4.9 Hz, 1H), 3.92 (t, JZ5.9 Hz, 1H), 1.02–
1.23 (m, 36H); 13C NMR (CDCl3): d 178.4, 177.5, 176.8,
176.7, 157.9, 150.0, 141.1, 129.5, 124.2, 91.6, 74.5, 72.9,
72.2, 68.0, 61.9, 39.0–39.1, 27.3–27.4; IR (KBr, cmK1): n
2940, 1735, 1600, 1578, 1528 1480, 1457, 1342, 832. Anal.
Calcd for C33H48N2O11: C, 61.10; H, 7.46; N, 4.32. Found:
C, 61.08; H, 7.49; N, 4.30.
90%; m/z (ESI): 631.4 [MCH]C; H NMR (CDCl3): d
7.70 (d, JZ7.2 Hz, 2H), 7.41 (t, JZ6.8 Hz, 2H), 7.31 (t, JZ
6.5 Hz, 1H), 5.45 (t, JZ9.4 Hz, 1H), 5.26 (t, JZ9.6 Hz,
1H), 5.14 (t, JZ9.2 Hz, 1H), 4.75 (d, JZ8.8 Hz, 1H), 4.58
(s, 1H) 4.29–4.32 (m, 2H), 3.92 (d, JZ1.6 Hz, 1H), 1.07–
1.33 (m, 36H); 13C NMR (CDCl3) d 178.5, 177.9, 176.8,
176.5, 130.1, 129.5, 128.8, 127.9, 114.2, 73.5, 72.3, 71.6,
68.2, 67.8.3, 66.8, 48.7, 39.0–39.2, 27.3–27.4; IR (KBr,
cmK1): n 2979, 2245, 1744, 1633, 1481, 1398, 1279, 1139,
1033, 941, 893. Anal. Calcd for C34H50N2O9: C, 64.74; H,
7.99; N, 4.44. Found: C, 64.73; H, 7.96; N, 4.47.
4.3.2. 4-Methyl-N-(2,3,4,6-tetra-O-pivaloylated-D-gluco-
pyranosyl)phenylglycinonitrile (3b). Mp 195–197 8C;
1
4.2.9. 3-Nitro-N-(2,3,4,6-tetra-O-pivaloylated-D-gluco-
pyranosyl)benzylideneamine (2i). Mp 211–213.9 8C;
yield 92%; m/z (ESI): 645.4 [MCH]C; H NMR (CDCl3):
d 7.63 (d, JZ7.9 Hz, 2H), 7.23 (d, JZ7.9 Hz, 2H), 5.73 (t,
JZ9.5 Hz, 1H), 5.56 (t, JZ9.6 Hz, 1H), 5.08 (t, JZ9.2 Hz,
1H), 4.86 (d, JZ8.8 Hz, 1H), 4.79 (s, 1H), 4.27 (d, JZ
10.9 Hz, 1H), 4.18 (q, JZ4.9 Hz, 1H), 3.80–3.82 (m, 1H),
2.39 (s, 3H), 1.03–1.25 (m, 36H); 13C NMR (CDCl3): d
178.4, 177.5, 176.7, 176.4, 142.2, 132.1, 129.7, 129.2,
114.7, 70.5, 68.9, 68.6, 60.7, 59.2, 58.2, 48.5, 39.6–39.4,
27.2–27.4, 21.8; IR (KBr, cmK1): n 2976, 2254, 1747, 1609,
1575, 147–81, 1398, 1368, 1138, 762. Anal. Calcd for
C35H52N2O9: C, 65.20; H, 8.13; N, 4.34. Found: C, 65.23;
H, 8.10; N, 4.13.
1
yield 96%; m/z (ESI): 649.2 [MCH]C; H NMR (CDCl3):
d 8.73 (s, 1H), 8.50 (s, 1H), 8.28 (d, JZ8.0 Hz, 1H), 7.99 (d,
JZ7.6 Hz, 1H), 7.60 (t, JZ7.8 Hz, 1H), 5.52 (t, JZ9.6 Hz,
1H), 5.22 (t, JZ9.6 Hz, 1H), 5.07 (d, JZ9.1 Hz, 1H), 4.95
(t, JZ9.3 Hz, 1H), 4.33 (d, JZ12 Hz, 1H), 4.19 (q, 1H),
3.93 (q, 1H), 1.04–1.26 (m, 36H); 13C NMR (CDCl3): d
178.3, 177.5, 176.9, 176.7, 157.3, 148.8, 137.5, 134.5,
129.9, 125.8, 123.2, 91.3, 77.5, 77.30, 77.0, 74.6, 72.9, 72.3,
68.1, 61.9, 27.33; IR (KBr, cmK1): n 2945, 1746, 1644,
1614, 1580, 1530, 1490, 1462, 1356, 794. Anal. Calcd for
C33H48N2O11: C, 61.10; H, 7.46; N, 4.32. Found: C, 61.11;
H, 7.43; N, 4.28.
4.3.3. 2-Hydroxyl-N-(2,3,4,6-tetra-O-pivaloylated-D-glu-
copyranosyl)phenylglycinonitrile (3c). Mp 205–208 8C;
yield 89%; m/z (ESI): 647.4 [MCH]C; 1H NMR (CDCl3): d
7.34 (t, JZ7.3 Hz, 1H), 7.28 (d, JZ8.0 Hz, 1H), 6.96 (d,
JZ8.2 Hz, 1H), 6.89 (t, JZ7.0 Hz, 1H), 5.61 (d, JZ9.6 Hz,
1H), 5.50 (t, JZ3.5 Hz, 1H), 5.34 (d, JZ9.9 Hz, 1H), 4.89
(s, 1H), 4.60 (d, JZ9.9 Hz, 1H), 4.13 (t, JZ4.4 Hz, 1H),
3.87 (d, JZ3.0 Hz, 1H), 3.75 (q, JZ1.5 Hz, 1H), 1.07–1.29
(m, 36H); 13C NMR (CDCl3): d 179.1, 178.9, 177.6, 176.3,
160.7, 134.4, 132.9, 119.7, 117.8, 113.3, 69.8, 68.3, 68.6,
67.2, 64.3, 60.3, 49.1, 39.0–39.2, 27.3–27.4. IR (KBr, cmK1):
n 3490, 2950, 2246, 1720, 1600, 1498, 1250, 1125, 750.
Anal. Calcd for C34H50N2O10: C, 63.14; H, 7.79; N, 4.33.
Found: C, 63.18; H, 7.75; N, 4.31.
4.2.10. N-(2,3,4,6-Tetra-O-pivaloylated-D-glucopyra-
nosyl)-2-furylideneamine (2j). Mp 95–98 8C; yield 90%;
1
m/z (ESI): 594.2 [MCH]C; H NMR (CDCl3): d 8.21 (s,
1H), 7.53 (d, JZ3.3 Hz, 1H), 6.86 (d, JZ2.5 Hz, 1H), 6.48
(t, JZ1.8 Hz, 1H), 5.45 (t, JZ9.4 Hz, 1H), 5.23 (t, JZ
9.6 Hz, 1H), 5.00 (t, JZ9.62 Hz, 1H), 4.88 (d, JZ8.6 Hz,
1H), 4.26 (d, JZ12 Hz, 1H), 4.16–4.18 (m, 1H), 3.89
(d, JZ5.8 Hz, 1H), 1.06–1.29 (m, 36H); 13C NMR (CDCl3):
d 178.4, 177.5, 176.6, 176.6, 151.6, 149.8, 145.8, 115.6,
112.3, 93.2, 74.5, 73.1, 72.3, 68.1, 62.1, 39.0–39.1, 27.3–
27.4; IR (KBr, cmK1): n 2974, 1741, 1648, 1480, 1397,
1368, 1283, 1140, 1070, 896, 761. Anal. Calcd For
C31H47NO10: C, 62.71; H, 7.98; N, 2.36. Found: C, 62.76;
H, 7.88; N, 2.38.
4.3.4. 4-Methoxy-N-(2,3,4,6-tetra-O-pivaloylated-D-glu-
copyranosyl)phenylglycinonitrile (3d). Mp 182–185 8C;
yield 85%; m/z (ESI): 661.4 [MCH]C; 1H NMR (CDCl3): d
7.76 (d, JZ8.4 Hz, 2H), 6.96 (d, JZ8.4 Hz, 2H), 5.74 (t,
JZ9.6 Hz, 1H), 5.28 (t, JZ9.6 Hz, 1H), 5.06 (t, JZ9.2 Hz,
1H), 4.81 (s, 1H), 4.26 (d, JZ5.3 Hz, 1H), 4.13–4.16 (m,
2H), 3.89 (s, 3H), 3.85 (d, JZ5.8 Hz, 1H), 1.04–1.22 (m,
36H); 13C NMR (CDCl3): d 178.4, 177.6, 177.3, 176.8,
162.8, 130.9, 128.0, 114.9, 114.3, 75.1, 74.4, 73.1, 72.2,
68.2, 62.2, 55.6, 49.5, 38.9–39.1, 27.2–27.4; IR(KBr, cmK1):
n 2976, 2246, 1739, 1607, 1580, 1520, 1481, 1396, 1284,
1254, 1150, 763. Anal. Calcd for C35H52N2O10: C, 63.62; H,
7.93; N, 4.24. Found: C, 63.58; H, 7.96; N, 4.21.
4.3. General procedure for the preparation of N-(2,3,4,6-
tetra-O-pivaloylated-D-glucopyranosyl)-amino nitriles
3a–j5
To
a
solution of trimethylsilylcyanide (0.186 g,
1.875 mmol) and cuprous bromide (0.488 g, 1.875 mmol)
in dichloromethane (20 mL) at 0 8C, a solution of imine 2
(1.5 mmol) in dichloromethane (1 mL) was added slowly.
After half an hour, the solution was allowed to slowly warm
to room temperature. The reaction was monitored by TLC,
after accomplished, the mixture was quenched with 2 N HCl
(10 mL) and washed with saturated aqueous NaHCO3
(10 mL!3) and water (10 mL). The organic layer was
dried over MgSO4 and concentrated in vacuo. The residue
4.3.5. 4-Chloro-N-(2,3,4,6-tetra-O-pivaloyl-D-glucopyra-
nosyl)phenylglycinonitrile (3e). Mp 210–212 8C; yield