A Facile Stereoselective Synthesis of (E)-1,2-Disubstituted Vinylic Selenides via Hydromagnesiation of Alkylarylacetylenes 67
(
E)-1-(4-Chlorophenyl)-1-(4-chlorophenylseleno)-
−
1
1
1
-hexene 4g. IR (film): ν (cm ) 2957, 2857, 1611,
589, 1487, 1473, 1386, 1090, 870, 813, 729; H NMR
1
(
1
CDCl
3
): δ 7.32–7.13 (m, 8H), 6.23 (t, J = 7.2 Hz,
H), 2.15–2.05 (m, 2H), 1.40–1.24 (m, 4H), 0.86
SCHEME 2
+
(
(
t, J = 6.8 Hz, 3H); MS: m/z 384 (M , 35.3), 193
29), 151 (94), 125 (100), 115 (75), 81 (67), 55 (72),
4
1 (47); anal. found: C, 56.04; H, 4.52. C18
H
18Cl Se
2
calc.: C, 56.25; H, 4.69%.
(
E)-1-Phenyl-1-(4-chlorophenylseleno)-1-hexene
−1
4
1
(
1
b. IR (film): ν (cm ) 3076, 3055, 3017, 2956, 2926,
1
(E)-1-Phenylseleno-1-(4-chlorophenyl)-1-hexene
596, 1574, 1488, 1472, 1386, 812, 760; H NMR
CDCl
): δ 7.38–7.12 (m, 9H), 6.17 (t, J = 7.6 Hz,
H), 2.11–2.05 (m, 2H), 1.37–1.21 (m, 4H), 0.83 (t,
−
1
4
h. IR (film): ν (cm ) 3071, 2957, 2857, 1611,
3
1
1
596, 1578, 1486, 1438, 870, 820, 737, 690; H NMR
+
(CDCl ): δ 7.43–7.21 (m, 9H), 6.21 (t, J = 7.6 Hz,
J = 6.8 Hz, 3H); MS: m/z 350 (M , 27.5), 159 (17),
3
1
H), 2.11–2.05 (m, 2H), 1.40–1.25 (m, 4H), 0.86 (t,
1
17 (100), 91 (90), 81 (47), 55 (23), 41 (22); anal.
+
J = 6.8 Hz, 3H); MS: m/z 350 (M , 53.7), 193 (46),
found: C, 61.52; H, 5.24. C18
H, 5.43%.
H19ClSe calc.: C, 61.71;
1
4
51 (100), 125 (86), 115 (72), 81 (90), 77 (44), 55 (62),
1 (52); anal. found: C, 61.48; H, 5.26. C18
H
19ClSe
calc.: C, 61.71; H, 5.43%.
(
E)-1-Phenyl-1-(4-bromophenylseleno)-1-hexene
−1
4
1
(
1
c. IR (film): ν (cm ) 3055, 3017, 2956, 2857,
597, 1565, 1488, 1466, 1380, 808, 760; H NMR
CDCl
1
(E)-1-(4-Chlorophenyl)-1-(4-bromophenylseleno)-
−
1
1
-hexene 4i. IR (film): ν (cm ) 2956, 2857, 1612,
3
): δ 7.29–7.08 (m, 9H), 6.18 (t, J = 7.6 Hz,
1
1
589, 1565, 1486, 1466, 1380, 870, 809, 709; H
H), 2.10–2.02 (m, 2H), 1.35–1.21 (m, 4H), 0.83 (t,
+
NMR (CDCl
3
): δ 7.42–7.14 (m, 8H), 6.22 (t, J = 7.6
J = 7.2 Hz, 3H); MS: m/z 394 (M , 17.4), 159 (28),
Hz, 1H), 2.09–2.03 (m, 2H), 1.37–1.23 (m, 4H), 0.84
1
17 (100), 91 (76), 81 (59), 55 (18), 41 (19); anal.
+
(
(
t, J = 6.8 Hz, 3H); MS: m/z 428 (M , 20.3), 193
found: C, 54.60; H, 4.63. C18
H, 4.82%.
H19BrSe calc.: C, 54.82;
23), 151 (86), 125 (100), 115 (74), 81 (66), 55 (79);
anal. found: C, 50.17; H, 4.05. C18
0.41; H, 4.20%.
H18ClBrSe calc.: C,
5
(E)-1-Phenyl-1-phenylseleno-1-octene 4d. IR
−
1
(
film): ν (cm ) 3057, 3017, 2924, 2854, 1577, 1489,
438, 1377, 761, 736, 699; H NMR (CDCl
(
E)-1-(4-Methoxyphenyl)-1-(4-chlorophenylsele
1
1
7
2
3
): δ 7.46–
−1
no)-1-octene 4j. IR (film): ν (cm ) 2926, 2855,
.20 (m, 10H), 6.16 (t, J = 7.6 Hz, 1H), 2.18–2.04 (m,
1
1
605, 1574, 1506, 1472, 813, 729; H NMR (CDCl ):
3
H), 1.40–1.20 (m, 8H), 0.87 (t, J = 6.8 Hz, 3H); MS:
δ 7.34–6.79 (m, 8H), 6.15 (t, J = 7.2 Hz, 1H), 3.80
+
m/z 344 (M , 18.4), 117 (83), 91 (100), 77 (18), 55
(
(
1
s, 3H), 2.18–2.05 (m, 2H), 1.39–1.20 (m, 8H), 0.88
(
15), 41 (38); anal. found: C, 69.72; H, 6.82. C20
calc.: C, 69.97; H, 7.00%.
H24Se
+
t, J = 6.8 Hz, 3H); MS: m/z 408 (M , 7.2), 217 (58),
47 (61), 121 (100); anal. found: C, 61.52; H, 5.98.
C H25ClOSe calc.: C, 61.76; H, 6.13%.
21
(
E)-1-Phenyl-1-(4-chlorophenylseleno)-1-octene
−1
4
2
(
1
e. IR (film): ν (cm ) 3077, 3056, 3018, 2925,
855, 1597, 1575, 1489, 1442, 813, 761, 699; H NMR
CDCl
(
E)-1-Phenylseleno-1-(4-methoxyphenyl)-1-octene
1
−1
4
k. IR (film): ν (cm ) 3057, 2926, 2854, 1603,
): δ 7.36–7.15 (m, 9H), 6.20 (t, J = 7.6 Hz,
1
3
1
577, 1506, 1475, 1464, 828, 736, 690; H NMR
H), 2.14–2.08 (m, 2H), 1.41–1.20 (m, 8H), 0.88 (t,
(
2
CDCl
3
): δ 7.45–7.17 (m, 7H), 6.78 (d, J = 8.8 Hz,
+
J = 6.8 Hz, 3H); MS: m/z 378 (M , 17.4), 117 (100),
H), 6.09 (t, J = 7.2 Hz, 1H), 3.77 (s, 3H), 2.15–2.05
1
5
05 (43), 91 (89), 41 (31); anal. found: C, 63.22; H,
23ClSe calc.: C, 63.49; H, 6.08%.
(
3
m, 2H), 1.36–1.15 (m, 8H), 0.85 (t, J = 6.8 Hz,
.89. C20
H
+
H); MS: m/z 374 (M , 10.8), 217 (70), 147 (61),
1
21 (100); anal. found: C, 67.30; H, 6.82. C21H26OSe
(
E)-1-Phenyl-1-(4-bromophenylseleno)-1-octene
calc.: C, 67.56; H, 6.97%.
−1
4
1
(
1
f. IR (film): ν (cm ) 3055, 3017, 2925, 2854, 1597,
565, 1488, 1466, 1379, 808, 760, 699; H NMR
CDCl
1
(E)-1-(4-Methylphenyl)-1-(4-chlorophenylseleno)-
1-hexene 4l. IR (film): ν (cm ) 3078, 3023, 2956,
2871, 1607, 1564, 1508, 1473, 814, 729; H NMR
−
1
3
): δ 7.38–7.15 (m, 9H), 6.21 (t, J = 7.6 Hz,
1
H), 2.15–2.06 (m, 2H), 1.41–1.21 (m, 8H), 0.89 (t,
+
J = 6.8 Hz, 3H); MS: m/z 422 (M , 13.4), 117 (100),
(CDCl
3
): δ 7.33–7.04 (m, 8H), 6.13 (t, J = 7.2 Hz,
1
5
05 (47), 91 (82), 41 (30); anal. found: C, 56.64; H,
23BrSe calc.: C, 56.87; H, 5.45%.
1H), 2.30 (s, 3H), 2.15–2.06 (m, 2H), 1.35–1.23 (m,
+
.28. C20
H
4H), 0.83 (t, J = 7.2 Hz, 3H); MS: m/z 364 (M , 23),