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J=2.6, 6.6 Hz), 3.86 (dd, 1H, J=3.6, 11.1 Hz), 3.48
(dd, 1H, J=10.6, 11.1 Hz), 3.28 (ddd, 1H, J=2.6, 4.3,
10.2 Hz), 3.13 (dd, 1H, J=10.2, 16.8 Hz), 2.57 (dd, 1H,
J=4.3, 16.8 Hz), 2.20 (br s, 1H), 1.16 (d, 3H, J=6.6
Hz). 13C NMR: l 139.9, 128.7 (two carbons), 128.4,
127.4 (two carbons), 118.3, 73.6, 72.9, 53.0, 52.8, 17.7,
15.7. MS m/z (rel. int.): 216 (4), 186 (4), 176 (8), 170
(7), 157 (6), 146 (100), 135 (26), 105 (27), 104, (86), 91
(25), 77 (15), 65 (3), 51 (5). Anal. calcd for C13H16N2O:
C, 72.19; H, 7.46, N, 12.95. Found: C, 72.23; H, 7.43;
N, 12.90%.
3.21. Methyl [(2S,3S,5R)-2-methyl-5-phenylmorpholin-
3-yl]acetate 8%b
Oil; [h]2D9=−65.6 (c 0.60, CHCl3). 1H NMR: l 7.45–7.25
(m, 5H), 4.04 (dd, 1H, J=3.3, 10.5 Hz), 3.84 (dd, 1H,
J=3.3, 11.1 Hz), 3.65 (s, 3H), 3.48 (dd, 1H, J=10.5,
11.1 Hz), 3.47–3.35 (m, 1H), 3.05 (dt, 1H, J=3.1, 9.3
Hz), 2.55 (dd, 1H, J=3.1, 16.3 Hz), 2.44 (dd, 1H,
J=9.3, 16.3 Hz), 2.40 (br s, 1H), 1.21 (d, 3H, J=6.2
Hz). 13C NMR: l 172.5, 139.9, 128.5 (two carbons),
127.9, 127.3 (two carbons), 75.3, 73.1, 60.2, 57.9, 51.8,
36.4, 17.8. MS m/z (rel. int.): 249 (3), 248 (3), 234 (2),
205 (9), 176 (30), 160 (8), 146 (34), 130 (12), 120 (13),
115 (21), 106 (25), 105 (20), 104, (100), 103 (12), 91 (14),
78 (13), 77 (12), 55 (7). Anal. calcd for C14H19NO3: C,
67.45; H, 7.68, N, 5.62. Found: C, 67.42; H, 7.69; N,
5.59%.
3.18. Methyl [(2S,3R,5R)-2-methyl-5-phenylmorpholin-
3-yl]acetate 7%b
1
Oil; [h]3D3=−7.4 (c 0.60, CHCl3). H NMR: l 7.48–7.20
(m, 5H), 4.20 (dd, 1H, J=3.4, 10.4 Hz), 4.05 (dq, 1H,
J=2.5, 6.6 Hz), 3.88 (dd, 1H, J=3.4, 11.0 Hz), 3.71 (s,
3H), 3.51 (dd, 1H, J=10.4, 11.0 Hz), 3.40 (ddd, 1H,
J=2.5, 3.8, 10.5 Hz), 3.06 (dd, 1H, J=10.5, 16.1 Hz),
2.56 (dd, 1H, J=3.8, 16.1), 2.52 (br s, 1H), 1.16 (d, 3H,
J=6.6 Hz). 13C NMR: l 173.3, 139.5, 128.5 (two
carbons), 127.9, 127.4 (two carbons), 74.0, 73.9, 53.2,
52.7, 51.8, 30.1, 17.8. MS m/z (rel. int.): 249 (2), 248
(2), 234 (2), 218 (4), 205 (11), 190 (4), 176 (26), 160 (13),
146 (28), 130 (10), 120 (20), 115 (24), 106 (28), 105 (22),
104 (100), 103 (13), 91 (15), 78 (11), 55 (9). Anal. calcd
for C14H19NO3: C, 67.45; H, 7.68, N, 5.62. Found: C,
67.51; H, 7.71; N, 5.59%.
3.22. [(2R,3R,5R)-2-Methyl-5-phenylmorpholin-3-yl]-
acetonitrile 9%a
Oil; [h]3D2=−14.1 (c 0.53, CHCl3). 1H NMR: l 7.53–7.48
(m, 2H), 7.30–7.25 (m, 3H), 4.14 (dd, 1H, J=4.4, 11.5
Hz), 4.08 (dd, 1H, J=3.4, 4.4 Hz), 3.89 (dd, 1H,
J=3.4, 11.5 Hz), 3.62 (quint, 1H, J=6.3 Hz), 3.0 (ddd,
1H, J=4.9, 6.3, 7.4 Hz), 2.63 (dd, 1H, J=7.4, 16.8 Hz),
2.54 (dd, 1H, J=4.9, 16.8 Hz), 2.0 (br s, 1H), 1.35 (d,
3H, J=6.3 Hz). 13C NMR: l 140.8, 128.6 (two car-
bons), 127.6, 127.5 (two carbons), 117.5, 74.1, 67.9,
54.2, 51.7, 21.7, 17.5. MS m/z (rel. int.): 216 (2), 185
(3), 172 (4), 157 (4), 146 (72), 139 (24), 135 (26), 134
(24), 117 (5), 105 (28), 104 (100), 103 (15), 91 (22), 78
(17), 77 (17), 65 (9), 51 (7). Anal. calcd for C13H16N2O:
C, 72.19; H, 7.46, N, 12.95. Found: C, 72.24; H, 7.44;
N, 12.99%.
3.19. Methyl [(2S,3R,5R)-2,5-diphenylmorpholin-3-yl]-
acetate 7%c
Oil; [h]2D5=−3.81 (c 0.83, CHCl3). 1H NMR: l 7.47–7.35
(m, 2H), 7.35–7.20 (m, 8H), 5.06 (d, 1H, J=2.8 Hz),
4.31 (dd, 1H, J=3.6, 10.6 Hz), 4.11 (dd, 1H, J=3.6,
11.1 Hz), 3.77 (ddd, 1H, J=2.8, 3.3, 11.1 Hz), 3.66 (dd,
1H, J=10.6, 11.1 Hz), 3.60 (s, 3H), 3.08 (dd, 1H,
J=11.1, 16.6 Hz), 2.35 (s, 1H), 2.06 (dd, 1H, J=3.3,
16.6 Hz). 13C NMR: l 173.6, 140.3, 139.7, 129.0 (two
carbons), 128.8 (two carbons), 128.6, 128.4, 127.8 (two
carbons), 125.8 (two carbons), 80.0, 74.9, 54.6, 53.1,
52.0, 30.1. Anal. calcd for C19H21NO3: C, 73.29; H,
6.80, N, 4.50. Found: C, 73.28; H, 6.75; N, 4.48%.
3.23. [(2R,3S,5R)-2-Methyl-5-phenylmorpholin-3-yl]-
acetonitrile 10%a
1
Oil; (slightly impure, [h] not determined). H NMR: l
7.48–7.25 (m, 5H), 4.02 (dd, 1H, J=4.3, 10.0 Hz), 4.01
(dq, 1H, J=3.7, 6.6 Hz), 3.61 (dd, 1H, J=10.0, 11.6
Hz), 3.56 (dd, 1H, J=4.3, 11.6 Hz), 3.55 (ddd, 1H,
J=3.7, 6.3, 8.3 Hz), 2.40 (dd, 1H, J=6.3, 16.6 Hz),
2.34 (dd, 1H, J=8.3, 16.6 Hz), 2.0 (br s, 1H), 1.39 (d,
3H, J=6.6 Hz). 13C NMR: l 139.3, 128.5 (two car-
bons), 127.9, 127.1 (two carbons), 117.1, 69.8, 65.5,
60.1, 53.1, 21.7, 10.9. MS m/z (rel. int.): 216 (2), 186
(3), 176 (5), 157 (6), 146 (100), 135 (25), 134 (19), 117
(6), 105 (26), 104, (91), 103 (14), 91 (21), 78 (13), 77
(14), 65 (3), 51 (5).
3.20. [(2S,3S,5R)-2-Methyl-5-phenylmorpholin-3-yl]-
acetonitrile 8%a
Oil; [h]3D1=−32.2 (c 0.60, CHCl3). 1H NMR: l 7.50–7.25
(m, 5H), 4.06 (dd, 1H, J=3.3, 10.4 Hz), 3.87 (dd, 1H,
J=3.3, 11.2 Hz), 3.44 (dd, 1H, J=10.4, 11.2 Hz), 3.41
(dq, 1H, J=6.2, 8.8 Hz), 2.96 (ddd, 1H, J=4.3, 7.3, 8.8
Hz), 2.54 (dd, 1H, J=4.3, 16.8 Hz), 2.46 (dd, 1H,
J=7.3, 16.8 Hz), 1.75 (br s, 1H), 1.26 (d, 3H, J=6.2
Hz). 13C NMR: l 139.3, 128.6 (two carbons), 128.4,
127.4 (two carbons), 116.9, 75.2, 72.5, 60.1, 56.9, 21.0,
17.6. MS m/z (rel. int.): 216 (2), 186 (3), 172 (6), 157
(5), 146 (88), 135 (29), 134, (27) 105 (27), 104, (100), 103
(13), 91 (23), 77 (16), 65 (3), 51 (6). Anal. calcd for
C13H16N2O: C, 72.19; H, 7.46, N, 12.95. Found: C,
72.22; H, 7.45; N, 12.97%.
3.24. Methyl [(2R,3S,5R)-2-methyl-5-phenylmorpholin-
3-yl]acetate 10%b
Oil; [h]3D0=−89.1 (c 2.10, CHCl3). 1H NMR: l 7.45–7.39
(m, 2H), 7.35–7.24 (m, 3H), 4.01 (dd, 1H, J=3.8, 10.4
Hz), 3.88 (dq, 1H, J=3.6, 6.6 Hz), 3.66 (s, 3H), 3.60
(dd, 1H, J=10.4, 11.4 Hz), 3.58 (ddd, 1H, J=3.6, 5.2,
8.5 Hz), 3.53 (dd, 1H, J=3.8, 11.4 Hz), 2.34 (dd, 1H,
J=5.2, 16.1 Hz), 2.30 (dd, 1H, J=8.5, 16.1 Hz), 2.20
(br s, 1H), 1.35 (d, 3H, J=6.6 Hz). 13C NMR: l 172.2,
140.6, 128.4 (two carbons), 127.7, 127.3 (two carbons),