One-Pot Synthesis of (E)-Disubstituted Alkenes
FULL PAPER
(Z)-1,2-Diphenylethylene (cis-stilbene) (4a): Prepared by method A
(silica gel, cyclohexane). Colorless oil; Rf =0.61 (silica gel, cyclohexane);
spectral data were identical to those of a commercial sample; 1H NMR
(300 MHz, CDCl3): d=6.75 (s, 2H), 7.34–7.40 ppm (m, 10H); 13C NMR
(75 MHz, CDCl3): d=127.1, 128.3, 128.9, 130.3, 137.3 ppm; MS: m/z: 180
[M]+.
Diphenylacetylene (5):[22] Obtained as a side product by method A (silica
gel, cyclohexane). White crystal; Rf =0.51 (silica gel, cyclohexane); spec-
tral data were identical to those of a commercial sample; m.p. 63–648C;
1H NMR (300 MHz, CDCl3): d=7.36–7.44 (m, 6H), 7.59–7.62ppm (m,
4H); 13C NMR (75 MHz, CDCl3): d=89.5, 123.4, 128.3, 128.4, 131.7 ppm;
MS: m/z: 178 [M]+.
(E)-3-(2-Hydroxyphenyl)propenal (4h): Prepared by method A (silica
gel, cyclohexane/ethyl acetate 7:3). Yield: 92%; yellow solid; Rf =0.18
(silica gel, cyclohexane/ethyl acetate 8:2); m.p. 122–1238C; 1H NMR
(300 MHz, CDCl3): d=6.17 (s, 1H), 6.87 (d, J=8.1 Hz, 1H), 6.94–7.01
(m, 2H), 7.32 (dt, J=1.5, 8.1 Hz, 1H), 7.52(d, J=7.8 Hz, 1H), 7.80 (d,
J=15.9 Hz, 1H), 9.69 ppm (d, J=8.1 Hz, 1H); 13C NMR (75 MHz,
MeOD): d=117.1, 120.8, 122.4, 129.3, 130.5, 133.8, 151.5, 158.7,
196.9 ppm; IR (KRS5): n˜ =1255, 1459 (#C=C), 1614, 1656 (#C=O),
+
3192cm À1 (#O H); MS: m/z: 149 [M+1] ; HRMS (EI): m/z: calcd for
À
C9H8O2: 148.1586 [M]+; found: 148.1582.
(E)-2-(3,3-Diethoxy-1-propenyl)pyrazine (4i): Prepared by method B
(silica gel, cyclohexane/ethyl acetate 7:3). Yield: 73%; yellow oil; Rf =
0.22 (silica gel, cyclohexane/ethyl acetate 8:2); 1H NMR (300 MHz,
CDCl3): d=1.26 (t, J=6.8 Hz, 6H), 3.58 (q, J=6.8 Hz, 2H), 3.72 (q, J=
6.8 Hz, 2H), 5.15 (d, J=2.5 Hz, 1H), 6.83 (d, J=2.2 Hz, 2H), 8.41 (d, J=
2.5 Hz, 1H), 8.51 (d, J=2.5 Hz, 1H), 8.59 ppm (s, 1H); 13C NMR
(75 MHz, CDCl3): d=13.7, 61.2, 103.5, 133.5, 139.1, 148.5, 149.3, 150.2,
156.3 ppm; IR (KRS5): n˜ =1058, 1130, 1397, 2928, 2975 cmÀ1; MS: m/z:
209 [M+1]+; HRMS (EI): calcd for C11H16N2O2: 208.2569 [M]+; found:
208.2565.
(E)-1-Methylalcohol-2-styrylbenzene (4b): Prepared by method A (silica
gel, cyclohexane/ethyl acetate 7:3). Yield: 95%; pink flakes; Rf =0.20
(silica gel, cyclohexane/ethyl acetate 8:2); m.p. 145–1468C; 1H NMR
(200 MHz, CDCl3): d=1.94 (brs, 1H), 4.86 (s, 2H), 7.10 (d, J=16.1 Hz,
1H), 7.18–7.74 ppm (m, 10H); 13C NMR (50 MHz, CDCl3): d=64.1,
125.9, 126.5, 127.3, 128.3, 128.4, 128.8, 129.1, 129.3, 131.7, 136.9, 138.0,
138.4 ppm. IR (KRS5): n˜ =1044, 1448, 1478, 1494, 3253, 3333 cmÀ1; MS:
m/z: 210 [M+]; HRMS (EI): m/z: calcd for C15H14O: 210.2711 [M]+;
found: 210.2709.
Ethyl(2 Z,4E)-6,6-diethoxy-2,4-hexadienoate (4j): Prepared by method A
(silica gel, cyclohexane/ethyl acetate 95:5). Yield: 90%; yellow oil; Rf =
0.56 (silica gel, cyclohexane/ethyl acetate 8:2); 1H NMR (200 MHz,
CDCl3): d=1.22 (t, J=7.1 Hz, 6H), 1.30 (t, J=7.1 Hz, 3H), 3.55 (q, J=
7.1 Hz, 2H), 3.65 (q, J=7.1 Hz, 2H), 4.20 (q, J=7.1 Hz, 2H), 4.99 (d, J=
5.6 Hz, 1H), 5.73 (d, J=11.2Hz, 1H), 5.97 (dd, J=5.6, 15.4 Hz, 1H),
6.57 (t, J=11.2Hz, 1H), 7.61 ppm (dd, J=11.2, 15.4 Hz, 1H); 13C NMR
(75 MHz, CDCl3): d=14.3, 15.3, 60.2, 61.6, 101.1, 119.5, 128.9, 139.0,
(E)-2-Styrylpyrazine (4c): Prepared by method B (silica gel, cyclohexane/
ethyl acetate 9:1). Yield: 75%; yellow oil; Rf =0.47 (silica gel, cyclohex-
ane/ethyl acetate 8:2); 1H NMR (200 MHz, CDCl3): d=7.19 (d, J=
16.1 Hz, 1H), 7.64 (dd, J=1.7, 8.1 Hz, 2H), 7.29–7.48 (m, 3H), 7.79 (d,
J=16.1 Hz, 1H), 8.44 (d, J=2.4 Hz, 1H), 8.57 (dd, J=1.2, 2.4 Hz, 1H),
8.68 ppm (d, J=1.2Hz, 1H); 13C NMR (75 MHz, CDCl3): d=124.1,
127.4, 128.9, 129.1, 135.3, 136.1, 142.8, 143.8, 144.4, 151.4 ppm; IR
(KRS5): n˜ =1396, 1449 (#C=C), 1494, 1636 cmÀ1 (#C=N); MS: m/z: 183
[M+1]+; HRMS (EI): m/z: calcd for C12H10N2: 182.2212 [M]+; found:
182.2209.
À
143.2, 166.2 ppm; IR (KRS5): n˜ =1190 (#C O), 1606, 1718 (#C=O),
2978 cmÀ1; MS: m/z: 2 2 8M[]+; HRMS (EI): m/z: calcd for C12H20O4:
228.2848 [M]+; found: 228.2845.
AHCTRE(GNU 2E,4E)-3-Methyl-5-phenyl-2,4-pentadien-1-ol (4k): Prepared by meth-
Ethyl( Z,E)-5-phenylpenta-2,4-dienoate (4d): Prepared by method A
(silica gel, cyclohexane/ethyl acetate 98:2). Yield: 93%; yellow oil; Rf =
0.23 (silica gel, cyclohexane/ethyl acetate 98:2); 1H NMR (300 MHz,
CDCl3): d=1.34 (t, J=7.2Hz, 3H), 4.24 (q, J=7.2Hz, 2H), 5.73 (d, J=
11.2Hz, 1H), 6.75 (t, J=11.2Hz, 1H), 6.83 (d, J=15.6 Hz, 1H), 7.29–
7.54 (m, 5H), 8.16 ppm (dd, J=11.2, 15.6 Hz, 1H); 13C NMR (75 MHz,
CDCl3): d=14.4, 60.1, 117.6, 125.0, 127.6, 128.8, 129.0, 136.5, 141.2, 144.8,
od A (silica gel, cyclohexane/ethyl acetate 8:2). Yield: 95%; pale-yellow
solid; Rf =0.26 (silica gel, cyclohexane/ethyl acetate 8:2); m.p. 125–
1268C; 1H NMR (75 MHz, CDCl3): d=1.93 (s, 3H), 4.36 (d, J=6.8 Hz,
2H), 5.82 ( t, J=6.8 Hz, 1H), 6.58 (d, J=16.2Hz, 1H), 6.82 (d, J=
16.2 Hz, 1H), 7.20–7.25 (m, 1H), 7.33 (t, J=7.2Hz, 2H), 7.43 ppm (d,
J=7.2Hz, 2H); 13C NMR (200 MHz, CDCl3): d=13.3, 60.1, 127.0, 128.0,
À
128.8, 129.2, 129.3, 131.6, 133.5, 137.0, 138.0 ppm; IR (KRS5): n˜ =1447
166.7 ppm; IR (KRS5): n˜ =1186 (#C O), 1450 (#C=C), 1624 (#C=C),
+
(#C=C), 1490, 2925, 3342 cmÀ1 (#O H); MS: m/z: 174 [M] ; HRMS
1711 cmÀ1 (#C=O); MS: m/z: 203 [M+1]+; HRMS (EI): m/z: calcd for
C13H14O2: 202.2491 [M]+; found: 202.2488.
À
(EI): m/z: calcd for C12H14O: 174.2390 [M]+; found: 174.2287.
A
(4l):
(E)-1-O-Tetrahydropyranyl-3-phenyl-2-propen-1-ol (4e): Prepared by
method A (silica gel, cyclohexane/ethyl acetate 98:2). Yield: 95%; yellow
oil; Rf =0.33 (silica gel, cyclohexane/ethyl acetate 95:5); 1H NMR
(300 MHz, CDCl3): d=1.54–1.88 (m, 6H), 3.55 (m, 1H), 3.93 (m, 1H),
4.18 (dd, J=6.5, 12.8 Hz, 1H), 4.42 (dd, J=5.6, 13.1 Hz, 1H), 4.73 (t, J=
4.0 Hz, 1H), 6.33 (dt, J=5.6, 15.9 Hz, 1H), 6.65 (d, J=15.9 Hz, 1H),
7.24–7.42 ppm (m, 5H); 13C NMR (CDCl3, 75 MHz): d=19.6, 25.6 30.7,
62.3, 67.7, 97.9, 126.1, 126.6, 127.7, 128.6, 132.4, 1369 ppm; IR (KRS5): n˜
Prepared by method B (silica gel, cyclohexane/ethyl acetate 7:3). Yield:
50%; yellow oil; Rf =0.21 (silica gel, cyclohexane/ethyl acetate 7:3);
1H NMR (300 MHz, CDCl3): d=1.88 (s, 3H), 2.34 (s, 3H), 2.43 (s, 3H),
4.34 (d, J=6.8 Hz, 2H), 5.75 (t, J=6.8 Hz, 1H), 6.18 (d, J=16.2Hz, 1H),
6.48 ppm (d, J=16.2Hz, 1H); 13C NMR (75 MHz, CDCl3): d=11.6, 11.9,
12.4, 59.4, 113.0, 115.7, 131.0, 134.5, 136.0, 158.4, 165.4 ppm; IR (KRS5):
n˜ =961, 1010, 1427, 3391 cmÀ1 (#O H); MS: m/z: 193 [M] ; HRMS (EI):
m/z: calcd for C11H15NO2: 193.2423 [M]+; found: 193.2425.
= 1025 (#C O), 1449 (#C=C), 1495, 2942 cmÀ1; MS: m/z: 219 [M+1]+;
À
HRMS (EI): m/z: calcd for C14H18O2: 218.2915 [M]+; found: 218.2912.
AHCTRE(GNU 2E,4E,6Z)-3-Methyl-8-ethyl ester-2,4,6-octatrien-1-ol (4m): Prepared by
method A (silica gel, cyclohexane/ethyl acetate 7:3). Yield: 95%; yellow
oil; Rf =0.33 (silica gel, cyclohexane/ethyl acetate 7:3); 1H NMR
(75 MHz, CDCl3): d=1.31 (t, J=7.2Hz, 3H), 1.88 (s, 3H), 4.20 (q, J=
7.2Hz, 2H), 4.35 (d, J=6.2Hz, 2H), 5.67 (d, J=11.2Hz, 1H), 5.85 (t,
J=6.2Hz, 1H), 6.51 (d, J=15.2Hz, 1H), 6.64 (t, J=11.2Hz, 1H),
7.59 ppm (dd, J=11.2, 15.2 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=
12.7, 14.4, 59.7, 60.0, 117.3, 124.8, 134.8, 136.3, 145.0, 145.3, 166.7 ppm;
(E)-1,3-Diphenyl-2-propenol (4 f): Prepared by method A (silica gel, cy-
clohexane/ethyl acetate 9:1). Yield: 96%; yellow oil; Rf =0.48 (silica gel,
cyclohexane/ethyl acetate 8:2); 1H NMR (CDCl3, 300 MHz): d=2.07
(brs, 1H), 5.41 (d, J=6.4 Hz, 1H), 6.41 (dd, J=6.4, 15.8 Hz, 1H), 6.71
(d, J=15.8 Hz, 1H), 7.20–7.44 ppm (m, 10H); 13C NMR (CDCl3,
75 MHz): d=75.5, 126.7, 127.0, 128.1, 128.2, 128.9, 129.0, 130.9, 131.9,
136.9, 143.1 ppm; IR (KRS5): n˜ = 1450 (#C=C), 1494, 3364 cmÀ1 (#O
À
IR (KRS5): n˜ =1185, 1614, 1711 (#C=O), 3411 cmÀ1 (#O H); MS: m/z:
H); MS: m/z: 210 [M]+; HRMS (EI): m/z: calcd for C15H14O: 210.2711
À
214 [M+18]+; HRMS (EI): m/z: calcd for C11H16O3: 196.2429 [M]+;
[M]+; found: 210.2715.
Trimethyl[2-(E)-phenylethenyl]silane (4g):[23] Prepared by method A
(silica gel, cyclohexane). Yield: 96%; yellow oil; Rf =0.71 (silica gel, cy-
clohexane/ethyl acetate 98:2); 1H NMR (300 MHz, CDCl3): d=0.19 (s,
9H), 6.51 (d, J=19.0 Hz, 1H), 6.91 (d, J=19.0 Hz, 1H), 7.27–7.48 ppm
(m, 5H); 13C NMR (75 MHz, CDCl3): d=À0.4, 127.1, 128.6, 129.2, 130.2,
139.0, 144.3 ppm; IR (KRS5): n˜ =843, 867, 1247, 1447, 1494, 1574, 1606,
2956 cmÀ1; MS: m/z: 176 [M]+; HRMS (EI): m/z: calcd for C11H16Si:
176.3302[ M]+; found: 176.3310.
found: 196.2425.
(E)-(1-Nonenyl)benzene (4n): Prepared by method A (silica gel, cyclo-
hexane). Yield: 85%; colorless oil; Rf =0.78 (silica gel, cyclohexane);
1H NMR (300 MHz, CDCl3): d=0.96 (t, J=7.1 Hz, 3H), 1.38 (m, 10H),
2.28 (m, 2H), 6.31 (dt, J=6.9, 15.0 Hz, 1H), 6,46 (d, J=15.1 Hz, 1H),
7.28–7.43 ppm (m, 5H); 13C NMR (75 MHz, CDCl3): d=14.1, 22.8, 29.5,
30.0, 31.9, 33.3, 125.8, 126.4, 128.0, 128.7, 129.0, 135.2 ppm; IR (KRS5):
n˜ =843, 956, 1032, 1447, 1462, 1512, 1606, 2958 cmÀ1; MS: m/z: 202 [M]+.
Chem. Eur. J. 2007, 13, 8971 – 8978
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
8977