Asymmetric Amidoselenenylation of Alkenes Promoted by Camphorselenenyl Sulfate
H), 7.8Ϫ7.7 (m, 2 H), 7.45Ϫ7.35 (m, 3 H), 4.26 (ddt, J ϭ 2.7, 8.9 J ϭ 4.7 Hz, 1 H), 3.20 (dt, J ϭ 3.7 and 7.1 Hz, 1 H), 2.2Ϫ2.1 (m,
FULL PAPER
and 11.0 Hz, 1 H), 3.5 (dd, J ϭ 2.4 and 4.6 Hz, 1 H), 3.3 (ddd, J ϭ
2.7, 5.5 and 9.1 Hz, 1 H), 2.16 (dd, J ϭ 4.2 and 4.6 Hz, 1 H),
2.0Ϫ1.5 (m, 7 H), 1.3 (ddd, J ϭ 5.4, 9.4 and 14.1 Hz, 1 H), 1.16
3 H), 2.0Ϫ1.0 (m, 14 H), 1.0 (s, 3 H), 0.95Ϫ0.9 (m, 9 H), 0.92 (s,
3 H), 0.85 (s, 3 H). Ϫ GC-MS m/z (%) ϭ 429 (2), 278 (13), 208 (5),
154 (16), 142 (32), 110 (31), 96 (15), 88 (35), 72 (100), 69 (22), 55
(t, J ϭ 7.3 Hz, 3 H), 1.08 (t, J ϭ 7.4 Hz, 3 H), 0.93 (s, 6 H), 0.82 (18), 43 (23).
(s, 3 H). Ϫ 13C NMR: δ ϭ 221.1, 167.7, 134.6, 131.6, 128.5, 127.9,
(4R,5S)-5-Benzamido-4-camphorselenenyloctane (8b): oil, [α]2D3
ϭ
58.0, 55.5, 55.0, 49.9, 49.5, 47.0, 30.8, 27.9, 23.7, 23.5, 19.6, 19.3,
13.6, 11.3, 10.0. Ϫ GC-MS: m/z (%) ϭ 435 (1), 350 (1), 314 (3),
284 (8), 232 (8), 204 (15), 162 (29), 122 (11), 105 (100), 83 (14), 77
(20), 41 (5). Ϫ C23H33NO2Se (434.48): calcd. C 63.19, H 7.76, N
3.22; found C 63.87, H 7.99, N 3.90.
1
ϩ24.4 (c ϭ 2.6, CHCl3). Ϫ H NMR: δ ϭ 8.01 (d, J ϭ 8.7 Hz, 1
H), 7.9Ϫ7.7 (m, 2 H), 7.5Ϫ7.25 (m, 3 H), 4.33 (ddt, J ϭ 11.2, 8.7
and 2.4 Hz, 1 H), 3.52 (dd, J ϭ 2.3 and 4.5 Hz, 1 H), 3.41 (ddd,
J ϭ 2.4, 5.9 and 8.9 Hz, 1 H), 2.14 (dd, J ϭ 4.1 and 4.5 Hz, 1 H),
1.9Ϫ1.1 (m, 12 H), 1.26 (s, 3 H), 0.98 (t, J ϭ 6.8 Hz, 6 H), 0.90 (s,
3 H), 0.8 (s, 3H ). Ϫ 13C NMR: δ ϭ 221.4, 167.5, 134.4, 131.7,
127.9, 127.2, 58.6, 53.6, 52.8, 49.9, 49.5, 47.1, 36.9, 32.7, 30.8, 23.4,
22.1, 19.9, 19.6, 19.2, 14.6, 14.3, 10.0. Ϫ GC-MS: m/z (%) ϭ 463
(1), 232 (15), 176 (29), 122 (11), 110 (19), 105 (100), 77 (18), 43 (3),
41 (5). Ϫ C25H37NO2Se (462.53): calcd. C 64.93, H 8.06, N 3.03;
found C 65.33, H 8.90, N 2.98.
(3S,4R)-4-Benzamido-3-camphorselenenylhexane (9a): oil, [α]2D3
ϭ
ϩ22.36 (c ϭ 0.9, CHCl3). Ϫ 1H NMR: δ ϭ 7.8Ϫ7.7 (m, 2 H),
7.5Ϫ7.3 (m, 3 H), 6.5 (d, J ϭ 9.3 Hz, 1 H), 4.3 (ddt, J ϭ 9.3, 10.7
and 3.7 Hz, 1 H), 3.7 (dd, J ϭ 1.2 and 3.3 Hz, 1 H), 3.26 (ddd, J ϭ
3.9, 6.7 and 10.7 Hz, 1 H), 1.99 (dd, J ϭ 3.3 and 3.9 Hz, 1 H),
1.8Ϫ1.2 (m, 8 H), 1.16 (t, J ϭ 7.3 Hz, 3 H), 1.0 (t, J ϭ 7.3 Hz, 3
H), 0.91 (s, 3 H), 0.89 (s, 3 H), 0.76 (s, 3 H). Ϫ 13C NMR: δ ϭ
217.4, 166.9, 134.7, 131.5, 128.6, 127.4, 58.1, 53.9, 52.6, 48.9, 48.5,
46.7, 30.4, 29.7, 27.6, 23.5, 23.3, 19.5, 13.1, 11.0, 9.7. Ϫ GC-MS:
m/z (%) ϭ 435 (1), 284 (11), 204 (23), 162 (29), 122 (17), 105 (100),
83 (12), 77 (20), 41 (5). Ϫ C23H33NO2Se (434.48): calcd. C 63.19,
H 7.76, N 3.22; found C 62.56, H 7.42, N 3.31.
(4S,5R)-5-Benzamido-4-camphorselenenyloctane (9b): oil, [α]2D3
ϭ
ϩ6.5 (c ϭ 2.0, CHCl3). Ϫ 1H NMR: δ ϭ 7.8Ϫ7.7 (m, 2 H), 7.5Ϫ7.3
(m, 3 H), 6.5 (d, J ϭ 9.1 Hz, 1 H), 4.35Ϫ4.25 (m, 1 H), 3.72 (d,
J ϭ 4.5 Hz, 1 H), 3.35 (ddd, J ϭ 3.6, 7.1 and 10.6 Hz, 1 H), 2.0 (t,
Jϭ 4.5 Hz, 1 H), 1.9Ϫ1.2 (m, 9 H), 1.25 (s, 3 H), 0.98 (t, J ϭ
7.0 Hz, 6 H), 0.91 (s, 3 H), 0.89 (s, 3 H), 0.75 (s, 3 H). Ϫ 13C NMR:
δ ϭ 217.8, 167.1, 134.9, 131.3, 129.0, 127.3, 58.5, 52.4, 50.9, 49.1,
49.0, 47.0, 37.1, 32.8, 30.8, 30.1, 23.7, 21.8, 19.9, 19.8, 14.4, 14.3,
10.1. Ϫ GC-MS: m/z (%) ϭ 463 (1), 312 (7), 232 (20), 176 (32), 105
(100), 72 (20). Ϫ C25H37NO2Se (462.53): calcd. C 64.93, H 8.06, N
3.03; found C 64.31, H 8.20, N 3.40.
(4R,5S)-5-Acetamido-4-camphorselenenyloctane (4b): oil, [α]2D3
ϭ
1
Ϫ53.7 (c ϭ 2.2, CHCl3). Ϫ H NMR: δ ϭ 7.57 (d, J ϭ 9.5 Hz, 1
H), 4.14 (dddd, J ϭ 2.5, 2.6, 8.5 and 9.5 Hz, 1 H), 3.50 (dd, J ϭ
2.4 and 4.6 Hz, 1 H), 3.1 (ddd, J ϭ 2.6, 5.4 and 8.5 Hz, 1 H), 2.27
(dd, J ϭ 4.3 and 4.6 Hz, 1 H), 1.9 (s, 3 H), 1.9Ϫ1.2 (m, 12 H), 1.02
(s, 3 H), 0.94 (s, 3 H), 0.93 (t, J ϭ 7.0 Hz, 3 H), 0.92 (t, J ϭ 7.0 Hz,
3 H), 0.87 (s, 3 H). Ϫ 13C NMR: δ ϭ 221.6, 170.4, 59.0, 55.1, 52.5,
50.4, 50.1, 47.2, 37.3, 33.1, 30.8, 23.7, 23.4, 22.0, 20.1, 19.7, 19.6,
14.5, 14.1, 10.2. Ϫ GC-MS: m/z (%) ϭ 401 (4), 342 (6), 250 (13),
232 (12), 191 (12), 170 (41), 152 (17), 128 (28), 126 (10), 114 (84),
110 (52), 81 (11), 72 (100), 69 (27), 60 (25), 55 (23), 43 (22), 41 (17).
Ϫ C20H35NO2Se (400.46): calcd. C 59.99, H 8.81, N 3.50; found C
59.88, H 8.89, N 3.47.
(5R,6S)-6-Acetamido-5-camphorselenenyldecane (4c): oil, [α]2D3
ϭ
Ϫ16.9 (c ϭ 1, CHCl3). Ϫ 1H NMR: δ ϭ 7.55 (d, J ϭ 9.6 Hz, 1 H),
4.12 (ddt, J ϭ 10.6, 9.6 and 2.5 Hz, 1 H), 3.49 (dd, J ϭ 2.0 and
4.2 Hz, 1 H), 3.06 (ddd, J ϭ 2.5, 4.9 and 9.2 Hz, 1 H), 2.27 (dd,
J ϭ 4.2 and 4.5 Hz, 1 H), 1.9 (s, 3 H), 1.8Ϫ1.2 (m, 16 H), 1.01 (s,
3 H), 0.94 (s, 3 H), 0.9 (t, J ϭ 7.1 Hz, 6 H), 0.86 (s, 3 H). Ϫ 13C
NMR: δ ϭ 221.5, 170.4, 58.8, 55.4, 52.8, 50.4, 50.1, 47.2, 34.9,
30.9, 30.8, 30.7, 30.1, 23.7, 23.4, 23.1, 22.8, 20.0, 19.6, 14.5, 14.4,
10.2. Ϫ GC-MS: m/z (%) ϭ 429 (4), 278 (9), 219 (10), 198 (38), 156
(23), 152 (16), 138 (55), 128 (13), 109 (16), 95 (12), 86 (100), 83
(31), 69 (22), 60 (28), 55 (34), 43 (34), 41 (27). Ϫ C22H39NO2Se
(428.51): calcd. C 61.67, H 9.17, N 3.27; found C 61.71, H 9.23,
N 3.25.
(4S,5R)-5-Acetamido-4-camphorselenenyloctane (5b): oil, [α]2D3
ϭ
1
ϩ30.6 (c ϭ 0.8, CHCl3). Ϫ H NMR: δ ϭ 5.77 (d, J ϭ 9.2 Hz, 1
H), 4.15 (ddt, J ϭ 9.7, 9.2 and 3.5 Hz, 1 H), 3.76 (d, J ϭ 4.6 Hz,
1 H), 3.22 (dt, J ϭ 3.6 and 7.4 Hz, 1 H), 2.15 (dd, J ϭ 4.4 and
4.6 Hz, 1 H), 2.02 (s, 3 H), 1.9Ϫ1.2 (m, 12 H), 1.04 (s, 3 H), 0.97
(t, J ϭ 7.2 Hz, 3 H), 0.94 (s, 3 H), 0.93 (t, J ϭ 7.3 Hz, 3 H), 0.92
(s, 3 H). Ϫ 13C NMR: δ ϭ 217.7, 169.7, 58.6, 52.1, 50.3, 49.2, 48.6,
47.2, 36.9, 33.1, 30.8, 24.0, 23.7, 21.8, 20.1, 19.9, 14.3, 10.1. Ϫ GC-
MS: m/z (%) ϭ 401 (5), 250 (14), 232 (11), 191 (11), 170 (64), 152
(18), 128 (38), 126 (10), 114 (87), 110 (44), 83 (11), 81 (11), 72 (100),
69 (30), 60 (43), 55 (26), 43 (24), 41 (18). Ϫ C20H35NO2Se (400.46):
calcd. C 59.99, H 8.81, N 3.50; found C 59.91, H 8.95, N 3.41.
(5S,6R)-6-Acetamido-5-camphorselenenyldecane (5c): oil, [α]2D3
ϭ
1
ϩ16.7 (c ϭ 0.5, CHCl3). Ϫ H NMR: δ ϭ 5.78 (d, J ϭ 9.0 Hz, 1
H), 4.1 (tt, J ϭ 3.5 and 9.0 Hz, 1 H), 3.72 (dd, J ϭ 1.5 and 4.5 Hz,
1 H), 3.18 (tt, J ϭ 3.5 and 7.7 Hz, 1 H), 2.11 (m, 1 H), 1.97 (s, 3
H), 1.8Ϫ1.2 (m, 16 H), 1.0 (s, 3 H), 0.9 (s, 3 H), 0.89 (t, J ϭ 7.0 Hz,
6 H), 0.88 (s, 3 H). Ϫ 13C NMR: δ ϭ 217.5, 169.7, 58.5, 52.3, 50.3,
49.2, 48.3, 47.1, 34.2, 30.8, 30.7, 30.6, 30.0, 28.8, 23.8, 23.7, 23.0,
22.9, 22.8, 20.0, 14.3, 10.0. Ϫ GC-MS: m/z (%) ϭ 429 (1), 278 (11),
232 (10), 219 (13), 198 (76), 152 (19), 138 (39), 128 (81), 109 (20),
95 (26), 86 (100), 83 (38), 60 (46), 55 (58), 43 (60), 41 (49). Ϫ
C22H39NO2Se (428.51): calcd. C 61.67, H 9.17, N 3.27; found C
61.66, H 9.21, N 3.33.
(4R,5S)-5-Butyramido-4-camphorselenenyloctane (6b): oil, [α]2D3
ϭ
Ϫ32.0 (c ϭ 4, CHCl3). Ϫ 1H NMR: δ ϭ 7.45 (d, J ϭ 9.5 Hz, 1 H),
4.15 (t, J ϭ 9.7 Hz, 1 H), 3.5 (dd, J ϭ 2.1 and 4.7 Hz, 1 H), 3.1Ϫ3.0
(m, 1 H), 2.26 (dd, J ϭ 4.1 and 4.7 Hz, 1 H), 2.2Ϫ2.05 (m, 2 H),
1.75Ϫ1.0 (m, 14 H), 1.01 (s, 3 H), 0.92 (t, J ϭ 7.0 Hz, 3 H), 0.94
(s, 3 H), 0.91 (t, J ϭ 7.3 Hz, 6 H), 0.86 (s, 3 H). Ϫ 13C NMR: δ ϭ
220.1, 172.9, 58.3, 54.7, 51.8, 50.0, 49.7, 46.7, 38.3, 36.9, 32.7, 30.3,
29.6, 23.3, 21.5, 19.5, 19.4, 19.3, 14.0, 13.7, 13.6, 9.7. Ϫ GC-MS:
m/z (%) ϭ 429 (2), 278 (12), 198 (26), 152 (11), 142 (29), 128 (19),
110 (40), 88 (20), 72 (100), 55 (14), 43 (17), 41 (11). Ϫ C22H39NO2Se
(428.51): calcd. C 61.67, H 9.17, N 3.27; found C 67.40, H 8.95,
N 3.10.
(2S)-2-Acetamido-2-phenyl-1-camphorselenenylethane (4d): oil,
[α]D19 ϭ ϩ24.4 (c ϭ 0.1, CHCl3). Ϫ 1H NMR: δ ϭ 7.85 (d, J ϭ 8.3 Hz,
1 H), 7.4Ϫ7.2 (m, 5 H), 5.54 (ddd, J ϭ 4.2, 4.5 and 8.3 Hz, 1 H),
3.5 (dd, J ϭ 2.2 and 4.7 Hz, 1 H), 3.4 (dd, J ϭ 4.2 and 13.3 Hz, 1
H), 3.17 (dd, J ϭ 4.5 and 13.3 Hz, 1 H), 2.22 (dd, J ϭ 4.3 and
4.7 Hz, 1 H), 2.1 (s, 3 H), 1.8Ϫ1.2 (m, 4 H), 1.02 (s, 3 H), 0.96 (s,
3 H), 0.87 (s, 3 H). Ϫ 13C NMR: δ ϭ 220.4, 169.7, 140.7, 128.3,
127.2, 126.5, 58.2, 51.7, 49.1, 48.8, 46.8, 34.0, 30.3, 23.2, 23.0, 19.6,
(4S,5R)-5-Butyramido-4-camphorselenenyloctane (7b): oil. Ϫ 1H
NMR: δ ϭ 5.7 (d, J ϭ 9.2 Hz, 1 H), 4.25Ϫ4.1 (m, 1 H), 3.72 (d,
Eur. J. Org. Chem. 2000, 3451Ϫ3457
3455