6284
K. Gu et al. / Bioorg. Med. Chem. 15 (2007) 6273–6290
Calcd for C11H14ClNO2: C, 58.03; H, 6.20; N, 6.15.
Found: C, 57.92; H, 6.09; N, 6.08.
3187, 3032, 1675, 1646, 1636, 1602, 1580, 1501, 1455,
1049, 741, 698. 1H NMR (500 MHz, CDCl3):
d/ppm = 8.003 (s, 2H), 7.548 (q, J = 7.10 Hz, 2H), 7.550
(t, J = 7.14 Hz, 2H), 7.302 (t, J = 7.14 Hz, 1H), 6.802 (d,
J = 13.00 Hz, 1H), 6.526 (d, J = 13.00 Hz, 1H), 5.634 (d,
J = 7.34 Hz, 1H), 4.638 (d, J = 11.51 Hz, 4H). 13C
NMR (CDCl3): d/ppm = 135.344, 128.612, 128.230,
127.174, 126.503, 124.326, 106.232, 73.603, 52.876.
FAB-MS (m/e) 206 [MH]+. Anal. Calcd for
C12H16ClNO2: C, 59.63; H, 6.67; N, 5.79. Found: C,
59.49; H, 6.58; N, 5.67.
4.11.19.
(2R,4S,5R)-2-[(40-Nitrophenyl)-4-methyl-1,3-
dioxan-5-yl]amine (50i). Yield: 95%. Mp 85–87 ꢁC.
IR(KBr): m/cmꢀ1 = 3255, 3189, 1647, 1636, 1602, 1580,
1523, 1502, 1455, 1382, 1350, 1048, 823. 1H NMR
(CDCl3): d/ppm = 8.316 (d, J = 9.00 Hz, 2H), 7.915 (d,
J = 9.00 Hz, 2H), 5.810 (s, 1H), 4.328 (m, J = 6.24 Hz,
1H), 4.387 (d, J = 5.74 Hz, 2H), 2.816 (m, J = 6.24 Hz,
1H), 1.738 (s, 2H), 1.334 (d, J = 6.34 Hz, 3H). 13C
NMR (DMSO-d6): d/ppm = 148.665, 144.984, 127.723,
123.752, 100.155, 76.726, 74.650, 49.216, 18.166. FAB-
4.11.24. (2R,4S,5R)-[2-(E-Phenylvinyl)-4-methyl-1,3-diox-
an-5-yl]amine (60b). Yield: 90%. Mp 82–84 ꢁC. IR(KBr):
m/cmꢀ1 = 3252, 3188, 3030, 1672, 1645, 1635, 1601,
1580, 1501, 1454, 1381, 1051, 741, 698. 1H NMR
(500 MHz, CDCl3): d/ppm = 7.993 (s, 2H), 7.596 (d,
J = 7.20 Hz, 2H), 7.560 (t, J = 7.20 Hz, 2H), 7.435 (t,
J = 7.20 Hz, 1H), 6.763 (d, J = 11.25 Hz, 1H), 6.538 (d ,
J = 11.22 Hz 1H), 5.559 (d, J = 6.00 Hz, 1H), 4.799 (m,
J = 4.74 Hz, 1H), 4.579 (d, J = 4.76 Hz, 2H), 3.993 (m,
J = 4.86 Hz, 1H), 1.387 (d, J = 4.86 Hz, 3H). 13C NMR
(CDCl3): d/ppm = 135.713, 128.714, 128.112, 127.394,
D
MS (m/e) 239 [M+H]+. ½aꢂ 10.8 (c 1.00, CHCl3). Anal.
20
Calcd for C11H14N2O2: C, 55.46; H, 5.92; N, 11.76.
Found: C, 55.58; H, 6.04; N, 11.82.
4.11.20. (2R,4S,5R)-2-[(30-Nitrophenyl)-4-methyl-1,3-diox-
an-5-yl]amine (50j). Yield: 95%. Mp 57–59 ꢁC. IR(KBr):
m/cmꢀ1 = 3252, 3189, 1647, 1636, 1602, 1580, 1524, 1500,
1
1456, 1382, 1350, 1049, 741, 698. H NMR (CDCl3):
d/ppm = 8.398 (s, 1H), 8.224 (d, J = 8.40 Hz, 1H), 8.012
(d, J = 7.80 Hz, 1H), 7.711 (t, J = 8.00 Hz, 1H), 5.725 (s,
1H), 4.317 (m, J = 4.32 Hz, 1H), 4.297 (d, J = 2.76 Hz,
2H), 2.656 (m, J = 3.24 Hz, 1H), 1.733 (s, 2H), 1.328 (d,
J = 4.66 Hz, 3H). 13C NMR (DMSO-d6): d/ppm =
148.627, 140.597, 132.588, 129.563, 124.222, 122.009,
126.587, 126.692, 105.835, 73.217, 72.946, 19.665. FAB-
D
MS (m/e) 220 [M+H]+. ½aꢂ 14.5 (c 1.0, H2O). Anal.
20
Calcd for C13H8ClNO2: C, 61.05; H, 7.09; N, 5.48.
Found: C, 61.16; H, 7.01; N, 5.36.
100.387, 76.552, 74.385, 49.083, 18.159. FAB-MS (m/e)
D
239 [M+H]+. ½aꢂ 13.2 (c 1.00, CHCl3). Anal. Calcd for
4.11.25. (2S,5S)-2-(40-Chlorophenyl-1,3-dioxaheptan-5-yl)-
amine (7c). Colorless powder, mp 48–49 ꢁC. IR(KBr):
m/cmꢀ1 = 3345, 3044, 2960, 2915, 2843, 1644, 1605, 1552,
1464, 1370, 1176, 1052, 821, 742, 691. 1H NMR (CDCl3):
d/ppm = 7.415 (d, J = 8.51 Hz, 2H), 7.326 (d, J = 8.51 Hz,
2H), 5.713 (s, 1H), 3.821 (d, J = 4.38 Hz, 2H), 3.543 (t,
J = 6.01 Hz, 2H), 3.089 (s, 1H), 1.889 (m, J = 3.72 Hz,
2H), 1.457 (s, 2H). 13C NMR (CDCl3): d/ppm = 147.886,
20
C11H14N2O2: C, 55.46; H, 5.92; N, 11.76. Found: C,
55.36; H, 6.03; N, 11.65.
4.11.21. (cis)-[2-(E-Phenylvinyl)-1,3-dioxan-5-yl]amine (6a).
Mp 65–67 ꢁC. IR(KBr): m/cmꢀ1 = 3249, 3188, 3030, 1673,
1645, 1635, 1601, 1581, 1500, 1457, 1048, 740, 696. H
1
NMR (500 MHz, CDCl3): d/ppm = 7.881 (s, 2H), 7.278
(q, J = 7.12 Hz, 2H), 7.263 (t, J = 7.16 Hz, 2H), 7.151 (t,
J = 7.16 Hz, 1H), 6.653 (d, J = 13.10 Hz, 1H), 6.257(d,
J = 13.10 Hz, 1H), 5.404 (d, J = 7.32 Hz, 1H), 4.443 (d,
J = 11.71 Hz, 4H). 13C NMR (CDCl3): d/ppm =
135.030, 128.323, 127.656, 126.867, 126.112, 123.967,
105.882, 73.287, 52.537. FAB-MS (m/e) 206 [M+H]+.
Anal. Calcd for C12H16ClNO2: C, 59.63; H, 6.67; N,
5.79. Found: C, 59.74; H, 6.81; N, 5.91.
146.407, 127.465, 123.383, 99.276, 69.684, 61.269, 49.879,
D
38.688. FAB-MS (m/e) 229 [M+H]+. ½aꢂ 8.0 (c 1.00,
20
CHCl3). Anal. Calcd for C11H12ClNO2: C, 58.03; H, 6.20;
N, 6.15. Found: C, 58.17; H, 6.09; N, 6.22.
4.11.26. (2R,5S)-2-(40-Chlorophenyl-1,3-dioxaheptan-5-
yl)amine (70c). Colorless powder, mp 56–57 ꢁC. IR(KBr):
m/cmꢀ1 = 3342, 3041, 2966, 2917, 2840, 1641, 1602, 1542,
1450, 1376, 1169, 1053, 822, 742, 694. 1H NMR (CDCl3):
d/ppm = 7.431 (d, J = 8.01 Hz, 2H), 7.334 (d,
J = 8.07 Hz, 2H), 5.695 (s, 1H), 3.894 (t, J = 3.22 Hz,
2H), 3.724 (d, J = 4.01 Hz, 2H), 3.134 (s, 1H), 2.023 (m,
J = 2.43 Hz, 2H), 1.602 (m, J = 3.52 Hz, 2H), 1.469 (s,
2H). 13C NMR (CDCl3): d/ppm = 147.886, 146.695,
4.11.22. (2S,4S,5R)-[2-(E-Phenylvinyl)-4-methyl-1,3-diox-
=
an-5-yl]amine (6b). Mp 77–79 ꢁC. IR(KBr): m/cmꢀ1
3250, 3190, 3031, 1675, 1644, 1636, 1602, 1581, 1503,
1455, 1380, 1049, 740, 696. 1H NMR (500 MHz, CDCl3):
d/ppm = 7.815 (s, 2H), 7.279 (d, J = 7.21 Hz, 2H), 7.246
(t, J = 7.22 Hz, 2H), 7.169 (t, J = 7.21 Hz, 1H), 6.565
(d, J = 11.87 Hz, 1H), 6.266 (d, J = 11.87 Hz 1H), 5.364
(d, J = 6.04 Hz, 1H), 4.597 (m, J = 4.71 Hz, 1H), 4.386
(d, J = 4.74 Hz, 2H), 3.816 (m, J = 4.84 Hz, 1H), 1.211
(d, J = 4.84 Hz, 3H). 13C NMR (CDCl3): d/ppm =
135.320, 128.401, 127.720, 127.072, 126.240, 126.187,
127.705, 123.651, 99.652, 70.574, 62.040, 50.462, 38.987.
D
FAB-MS (m/e) 229 [M+H]+. ½aꢂ ꢀ6.0 (c 1.00, CHCl3).
20
Anal. Calcd for C11H12ClNO2: C, 58.03; H, 6.20; N,
6.15. Found: C, 58.12; H, 6.19; N, 6.27.
4.11.27. (2S,5S)-2-(40-Nitrophenyl-1,3-dioxaheptan-5-yl)-
amine (7d). Colorless powder, mp 76–78 ꢁC. IR(KBr):
m/cmꢀ1 = 3345, 3042, 2970, 2919, 2851, 1642, 1600,
1561, 1521, 1462, 1372, 1352, 1171, 1050, 821, 742, 693.
1H NMR (CDCl3): d/ppm = 8.216 (d, J = 9.04 Hz, 2H),
7.665 (d, J = 8.52 Hz, 2H), 5.793 (s, 1H), 3.862 (d,
J = 4.31 Hz, 2H), 3.610 (t, J = 6.04 Hz, 2H), 3.153 (s,
1H), 1.821 (s, 2H), 1.789 (t, J = 3.95 Hz, 2H). 13C NMR
105.543, 72.805, 72.684, 19.285. FAB-MS (m/e) 220
D
[M+H]+. ½aꢂ ꢀ12.0 (c 1.0, H2O). Anal. Calcd for
20
C13H8ClNO2: C, 61.05; H, 7.09; N, 5.48. Found: C,
61.12; H, 7.17; N, 5.53.
4.11.23. (trans)-[2-(E-Phenylvinyl)-1,3-dioxan-5-yl]amine
(60a). Yield: 90%. Mp 70–72 ꢁC. IR(KBr): m/cmꢀ1 = 3252,