R. M. Kellogg et al.
FULL PAPER
5.67Ϫ5.81 (m, 1 H), 6.12 (br. s, 1 H), 7.05Ϫ7.11 (m, 5 H), 175.6 (s) ppm. C18H19FN2 (282.4): calcd. C 72.46, H 6.42, N 9.39;
7.16Ϫ7.24 (m, 5 H) ppm. 13C NMR (50 MHz, CDCl3): δ ϭ 18.6
(q), 40.0 (t), 59.0 (d), 61.9 (d), 115.2 (t), 124.4 (d), 124.8 (d), 125.6
(d), 126.3 (d), 126.8 (d), 132.6 (d), 134.6 (s), 136.8 (s), 136.9 (s),
173.7 (s) ppm. C19H22N2O (294.4): calcd. C 77.52, H 7.53, N 9.52;
found C 77.43, H 7.42, N 9.34. MS (CI): m/z ϭ 295 [M ϩ Hϩ].
found C 72.19, H 6.30, N 9.51. MS (CI): m/z ϭ 299 [M ϩ Hϩ].
(2R)-2-{[(1R)-1-(4-Fluorophenyl)-3-butenyl]amino}-2-phenylethan-
amide (33): Yellow oil, which crystallises on standing, 94% yield,
1
99:1 dr). H NMR (300 MHz, CDCl3): δ ϭ 2.14 (br. s, 2 H), 2.35
(t, J ϭ 7.0 Hz, 2 H), 3.65 (t, J ϭ 7.0 Hz, 1 H), 3.88 (s, 1 H),
4.99Ϫ5.05 (m, 2 H), 5.58Ϫ5.69 (m, 1 H), 6.44 (br. s, 1 H), 6.96 (t,
J ϭ 8.7 Hz, 2 H), 7.08Ϫ7.12 (m, 4 H), 7.18Ϫ7.22 (m, 4 H) ppm.
13C NMR (50 MHz, CDCl3): δ ϭ 42.3 (t), 61.3 (d), 64.3 (d), 115.5
(d, 2JC,F ϭ 13.8 Hz), 118.2 (t), 127.2 (d), 128.3 (d), 128.7 (d, 3JC,F ϭ
(2R)-2-{[(1R)-1-(2-Methoxyphenyl)-3-butenyl]amino}-2-phenyl-
ethanamide (28): Pale yellow solid, 98% yield, Ͼ99:1 dr. M.p.
63.1Ϫ63.8 °C. 1H NMR (300 MHz, CDCl3): δ ϭ 2.38 (d, J ϭ
7.0 Hz, 2 H), 3.62 (t, J ϭ 7.0 Hz, 1 H), 3.76 (s, 3 H), 3.95 (s, 1 H),
5.00Ϫ5.07 (m, 2 H), 5.65Ϫ5.79 (m, 2 H), 5.97 (br. s, 1 H), 6.81 (d,
J ϭ 8.6 Hz, 2 H), 7.03 (br. s, 1 H), 7.07 (d, J ϭ 8.6 Hz, 2 H), 7.14
Ϫ7.26 (m, 3 H) ppm. 13C NMR (50 MHz, CDCl3): δ ϭ 40.2 (t),
54.9 (q), 64.7 (d), 110.7 (d), 117.1 (t), 120.5 (d), 127.2 (d), 127.9
(d), 128.4 (d), 128.6 (d), 129.5 (s), 135.7 (d), 139.4 (s), 157.3 (s),
176.3 (s) ppm. C19H22N2O2·1/2H2O: calcd. C 71.45, H 7.26, N 8.77;
found C 71.43, H 6.88, N 8.76. MS (CI): m/z ϭ 311 [M ϩ Hϩ].
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5.7 Hz), 134.3 (d), 138.6 (s), 137.7 (s), 162.1 (s, JC,F ϭ 162.7 Hz),
175.8 (s) ppm. MS (CI): m/z ϭ 299 [M ϩ Hϩ].
(2R)-2-{[(1R)-1-(2-Chlorophenyl)-3-butenyl]amino}-2-phenylethan-
amide (34): Pale yellow oil, which crystallises on standing, 98%
1
yield, 97:3 dr. M.p. 110.4Ϫ111.0 °C. H NMR (300 MHz, CDCl3):
δ ϭ 2.32Ϫ2.52 (m ϩ br. s, 3 H), 3.89 (s, 1 H), 4.25 (t, J ϭ 6.8 Hz,
1 H), 4.99Ϫ5.10 (m, 2 H), 5.68Ϫ5.82 (m, 1 H), 6.55 (br. s, 1 H),
7.04 (br. s, 1 H), 7.12Ϫ7.30 (m, 9 H) ppm. 13C NMR (50 MHz,
CDCl3): δ ϭ 40.7 (t), 58.2 (d), 64.5 (d), 118.1 (t), 127.0 (d), 127.2
(d), 127.7 (d), 128.1 (d), 128.4 (d), 128.8 (d), 129.9 (d), 133.8 (s),
134.4 (d), 138.9 (s), 139.4 (s), 175.6 (s) ppm. C18H19ClN2O (314.8):
calcd. C 68.67, H 6.08, N 8.90; found C 68.51, H 6.29, N 8.75. MS
(CI): m/z ϭ 315 [M ϩ Hϩ]. MS (CI): m/z ϭ 315 (100.0) [M ϩ Hϩ],
317 (35.8) [M ϩ Hϩ].
(2R)-2-{[(1R)-1-(3-Methoxyphenyl)-3-butenyl]amino}-2-phenyl-
ethanamide (29): Pale yellow solid, 99% yield, Ͼ99:1 dr. M.p.
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96.6Ϫ97.2 °C. H NMR (300 MHz, CDCl3): δ ϭ 2.08 (br. s, 1 H),
2.38 (d, J ϭ 7.0 Hz, 1 H), 3.65 (t, J ϭ 7.0 Hz, 1 H), 3.73 (s, 3 H),
3.97 (s, 1 H), 5.02Ϫ5.09 (m, 2 H), 5.68Ϫ5.81 (m, 1 H), 5.98 (br. s,
1 H), 6.70Ϫ6.77 (m, 3 H), 6.99 (br. s, 1 H), 7.17Ϫ7.26 (m, 6 H)
ppm. 13C NMR (50 MHz, CDCl3): δ ϭ 42.2 (t), 54.8 (q), 61.3 (d),
64.0(d), 112.4(d), 112.5 (d), 117.4 (t), 119.1 (d), 127.0 (d), 127.7 (d),
128.4 (d), 129.3 (d), 134.7 (d), 139.2 (s), 144.2 (s), 159.5 (s), 175.7 (s)
ppm. C19H22N2O2·1/2H2O: calcd. C 71.45, H 7.26, N 8.77; found C
71.45, H 6.90, N 8.79. MS (CI): m/z ϭ 311 [M ϩ Hϩ].
(2R)-2-{[(1R)-1-(3-Chlorophenyl)-3-butenyl]amino}-2-phenylethan-
amide (35): (white plates, 83% yield, 98:2 dr. M.p. 39.2Ϫ40.3 °C.
1H NMR (200 MHz, CDCl3): δ ϭ 2.15 (br. s, 1 H), 2.33 (d, J ϭ
6.8 Hz, 2 H), 3.63 (t, J ϭ 6.8 Hz, 1 H), 3.88 (s, 1 H), 4.97Ϫ5.05
(m, 2 H), 5.55Ϫ5.75 (m, 1 H), 6.54 (br. s, 1 H), 6.82 (br. s, 1 H),
6.97Ϫ7.24 (m, 8 H) ppm. 13C NMR (50 MHz, CDCl3): δ ϭ 42.4
(t), 61.3 (d), 64.3 (d), 118.2 (t), 125.2 (d), 127.1 (d), 127.6 (d), 128.2
(d), 128.8 (d), 129.8 (d), 134.2 (d), 134.4 (s), 138.9 (s), 144.8 (s),
175.5 (s) ppm. C18H19ClN2O (314.8): calcd. C 68.67, H 6.08, N
8.90; found C 68.32, H 6.16, N 8.76. MS (CI): m/z ϭ 315 (100.0)
[M ϩ Hϩ], 317 (35.0) [M ϩ Hϩ].
(2R)-2-{[(1R)-1-(4-Methoxyphenyl)-3-butenyl]amino}-2-phenyl-
ethanamide (30): Pale yellow solid, 99% yield, Ͼ99:1 dr. M.p.
92.2Ϫ92.7 °C. 1H NMR (300 MHz, CDCl3): δ ϭ 2.38 (d, J ϭ
7.0 Hz, 2 H), 3.62 (t, J ϭ 7.0 Hz, 1 H), 3.76 (s, 3 H), 3.95 (s, 1 H),
5.00Ϫ5.07 (m, 2 H), 5.65Ϫ5.79 (m, 2 H), 5.97 (br. s, 1 H), 6.81 (d,
J ϭ 8.6 Hz, 2 H), 7.03 (br. s, 1 H), 7.07 (d, J ϭ 8.6 Hz, 2 H), 7.14
Ϫ7.26 (m, 3 H) ppm. 13C NMR (50 MHz, CDCl3): δ ϭ 42.1 (t),
55.0 (q), 60.9 (d), 63.9 (d), 113.7 (t), 117.4 (t), 127.1 (d), 127.8 (d),
128.0 (d), 128.6 (d), 134.0 (s), 134.7 (d), 138.9 (s), 158.6 (s), 176.0
(s) ppm. C19H22N2O2 (310.4): calcd. C 73.52, H 7.10, N 9.00; found
C 73.70, H 6.95, N 9.04. MS (CI): m/z ϭ 311 [M ϩ Hϩ].
(2R)-2-{[(1R)-1-(4-Chlorophenyl)-3-butenyl]amino}-2-phenylethan-
amide (36): Yellow solid, 98% yield, Ͼ99:1 dr. M.p. 111.3Ϫ112.0
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°C. H NMR (300 MHz, CDCl3): δ ϭ 2.33Ϫ2.47 (m ϩ br. s, 3 H),
3.71 (t, J ϭ 7.0 Hz, 1 H), 3.97 (s, 1 H), 5.58Ϫ5.72 (m, 2 H), 5.99
(br. s, 1 H), 6.80 (br. s, 1 H), 7.06Ϫ7.13 (m, 4 H), 7.21Ϫ7.24 (m, 5
H) ppm. 13C NMR (50 MHz, CDCl3): δ ϭ 42.2 (t), 61.3 (d), 64.3
(d), 118.4 (t), 127.2 (d), 128.4 (d), 128.5 (d), 128.8 (d), 129.0 (d),
133.3 (s), 124.1 (d), 138.5 (s), 175.5 (s), 140.5 (s) ppm.
C18H19ClN2O (314.8): calcd. C 68.67, H 6.08, N 8.90; found C
68.24, H 5.88, N 8.63. MS (CI): m/z ϭ 315 (100.0) [M ϩ Hϩ], 317
(35.7) [M ϩ Hϩ].
(2R)-2-{[(1R)-1-(2-Fluorophenyl)-3-butenyl]amino}-2-phenylethan-
amide (31): Pale yellow oil, which crystallises on standing, Ͼ99%
yield, 98:2 dr. H NMR (300 MHz, CDCl3): δ ϭ 2.20 (br. s, 1 H),
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2.46 (dt, J ϭ 7.0 Hz, 2 H), 3.94 (s, 1 H), 3.99 (t, J ϭ 7.0 Hz, 1
H), 5.02Ϫ5.09 (m, 2 H), 5.69Ϫ5.83 (m, 1 H), 6.95Ϫ7.08 (m, 3 H),
7.13Ϫ7.28 (m, 8 H) ppm. 13C NMR (50 MHz, CDCl3): δ ϭ 40.9
2
(t), 56.3 (d), 64.6 (d), 115.6 (d, JC,F ϭ 22.0 Hz), 117.8 (t), 124.1
(d, 4JC,F ϭ 3.7 Hz), 127.02 (d), 127.9 (d), 128.3 (d, 3JC,F ϭ 4.9 Hz),
3
(2R)-2-{[(1R)-1-(2-Bromophenyl)-3-butenyl]amino}-2-phenylethan-
amide (37): Pale yellow oil, 98% yield, Ͼ99:1 dr). 1H NMR
(300 MHz, CDCl3): δ ϭ 2.24Ϫ2.50 (m ϩ br. s, 3 H), 3.88 (s, 1 H),
4.24 (dd, J ϭ 8.1, J ϭ 5.1 Hz, 1 H), 5.05Ϫ5.15 (m, 2 H), 5.71Ϫ5.83
(m, 1 H), 6.45 (br. s, 1 H), 6.99 (br. s, 1 H), 7.06 (dt, J ϭ 7.5, J ϭ
1.8 Hz, 1 H), 7.16Ϫ7.24 (m, 7 H), 7.49 (d, J ϭ 7.7 Hz, 1 H) ppm.
13C NMR (50 MHz, CDCl3): δ ϭ 38.6 (t), 57.7 (d), 62.0 (d), 115.7
(d), 121.9 (d), 124.8 (d), 125.2 (t), 125.5 (d), 125.6 (d), 126.3 (d),
126.3 (d), 130.7 (d), 132.1 (d), 136.8 (s), 138.9 (s), 173.1 (s) ppm.
C18H19BrN2O (359.3): calcd. C 60.18, H 5.33, N 7.80; found C
60.02, H 5.06, N 8.07. MS (CI): m/z ϭ 359 (39.8) [M ϩ Hϩ], 361
(39.4) [M ϩ Hϩ].
128.6 (d), 128.8 (d), 129.2 (s, JC,F ϭ 12.2 Hz), 134.6 (d), 139.1 (s),
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160.91 (s, JC,F ϭ 245.4 Hz), 175.6 (s) ppm. C18H19FN2·1/2H2O:
calcd. C 70.34, H 6.56, N 9.11; found C 70.63, H 6.17, N 9.39. MS
(CI): m/z ϭ 299 [M ϩ Hϩ].
(2R)-2-{[(1R)-1-(3-Fluorophenyl)-3-butenyl]amino}-2-phenylethan-
amide (32): Yellow oil, which crystallises on standing, 97% yield,
1
98:2 dr). H NMR (300 MHz, CDCl3): δ ϭ 2.20 (br. s, 1 H), 2.37
(d, J ϭ 7.0 Hz, 2 H), 3.68 (t, J ϭ 7.0 Hz, 1 H), 3.92 (s, 1 H),
5.01Ϫ5.07 (m, 2 H), 5.63Ϫ5.76 (m, 1 H), 6.71 (br. s, 1 H),
6.87Ϫ6.95 (m, 4 H), 7.15Ϫ7.26 (m, 6 H) ppm. 13C NMR (50 MHz,
2
CDCl3): δ ϭ 42.3 (t), 61.1 (d), 64.3 (d), 113.7 (d, JC,F ϭ 20.8 Hz),
2
3
114.2 (d, JC,F ϭ 22.0 Hz), 118.0 (t), 122.7 (d, JC,F ϭ 2.4 Hz),
3
127.1 (d), 128.1 (d), 128.8 (d), 130.0 (d, JC,F ϭ 8.6 Hz), 134.4 (d),
139.0 (s), 145.5 (s, JC,F ϭ 7.3 Hz), 163.0 (s, JC,F ϭ 246.6 Hz),
(2R)-2-{[(1R)-1-(3-Bromophenyl)-3-butenyl]amino}-2-phenylethan-
amide (38): Pale yellow oil, 99% yield, Ͼ99:1 dr). 1H NMR
3
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2004, 1544Ϫ1557