BiCl3-catalyzed Hydroarylation of Styrenes with Electron-Rich Arenes
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H), 3.74 (s, 3 H), 1.53 (d, J = 6.9 Hz, 3 H) ppm. 13C NMR (d, J = 8.6 Hz, 2 H), 6.59 (s, 1 H), 6.53 (s, 1 H), 4.56 (q, J = 7.2 Hz,
(75 MHz, CDCl3): δ = 157.1, 143.9, 134.0, 133.6, 129.4, 128.3, 1 H), 3.57 (s, 3 H), 2.28 (s, 3 H), 2.18 (s, 3 H), 1.61 (d, J = 7.2 Hz,
127.4, 127.3, 127.0, 126.5, 120.3, 110.6, 55.5, 34.9, 19.9 ppm. GC–
MS: m/z (%) 246 (100) [M]+, 231 (80), 211 (56), 181 (30), 165 (71),
152 (39), 125 (91), 91 (20).
3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 157.8, 144.6, 136.9,
136.8, 130.6, 129.9, 128.4, 127.7, 124.2, 110.6, 55.3, 35.5, 21.3, 20.5,
17.3 ppm. GC–MS: m/z (%) 274 (45) [M]+, 259 (56), 179 (25), 165
(24), 125 (100), 91 (13), 77 (16). HRMS: calcd. for C17H19ClO
274.1124; found 274.1129.
1-(2-Chlorophenyl)-1-(4-ethoxyphenyl)ethane (3i): 1H NMR
(300 MHz, CDCl3): δ = 7.20–6.80 (m, 8 H), 4.59 (q, J = 7.2 Hz, 1
H), 3.99 (q, J = 6.9 Hz, 2 H), 1.57 (d, J = 7.2 Hz, 3 H), 1.38 (t, J
= 6.9 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 157.3, 144.1,
136.9, 133.7, 129.5, 128.6, 128.5, 127.2, 126.9, 114.2, 63.3, 40.1,
21.2, 14.9 ppm. GC–MS: m/z (%) 260 (42) [M]+, 245 (100), 217
(61), 181 (33), 152 (38), 91 (7), 77 (13). HRMS: calcd. for
C16H17ClO 260.0968; found 260.0957.
1-(2-Chlorophenyl)-1-(2-ethoxyphenyl)ethane (3iЈ): 1H NMR
(300 MHz, CDCl3): δ = 7.30–6.80 (m, 8 H), 4.91 (q, J = 7.2 Hz, 1
H), 3.83 (q, J = 6.9 Hz, 2 H), 1.53 (d, J = 7.2 Hz, 3 H), 1.24 (t, J
= 6.9 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 156.5, 144.5,
133.9, 133.6, 129.2, 128.3, 127.32, 127.27, 126.8, 126.5, 120.1,
111.4, 63.6, 35.0, 19.8, 14.7 ppm. GC–MS: m/z (%) 260 (87) [M]+,
245 (12), 231 (48), 181 (100), 152 (76), 139 (63), 107 (76), 91 (33).
1-(4-Chlorophenyl)-1-(4-methoxy-2,6-dimethylphenyl)ethane (3mЈ):
1H NMR (300 MHz, CDCl3): δ = 7.21 (d, J = 8.6 Hz, 2 H), 7.09
(d, J = 8.6 Hz, 2 H), 6.55 (s, 2 H), 4.53 (q, J = 7.2 Hz, 1 H), 3.77
(s, 3 H), 2.11 (s, 6 H), 1.62 (d, J = 7.2 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 157.4, 144.2, 137.8, 134.9, 131.0, 128.2,
114.4, 111.6, 55.0, 37.0, 21.4, 17.1 ppm. GC–MS: m/z (%) 274 (34)
[M]+, 259 (100), 209 (15), 165 (24), 103 (11), 91 (10), 77 (11).
1-(2,4,6-Trimethylphenyl)-1-phenylethane (3n): 1H NMR (300 MHz,
CDCl3): δ = 7.30–7.10 (m, 5 H), 6.82 (s, 2 H), 4.63 (q, J = 7.2 Hz,
1 H), 2.25 (s, 3 H), 2.10 (s, 6 H), 1.65 (d, J = 7.2 Hz, 3 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 145.4, 140.0, 136.5, 135.4, 130.0,
128.1, 126.8, 125.2, 37.8, 21.0, 20.7, 16.8 ppm. GC–MS: m/z (%)
224 (100) [M]+, 209 (100), 179 (33), 165 (14), 91 (6), 77 (7).
1-(4-Methoxyphenyl)-1-(2-methylphenyl)ethane (3j): 1H NMR
(300 MHz, CDCl3): δ = 7.26–7.15 (m, 4 H), 7.05 (d, J = 8.6 Hz, 2
H), 6.79 (d, J = 8.6 Hz, 2 H), 4.26 (q, J = 6.9 Hz, 1 H), 3.76 (s, 3
H), 2.23 (s, 3 H), 1.57 (d, J = 6.9 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 157.7, 144.3, 138.4, 136.0, 130.4, 128.5 (2C),
126.5, 126.0, 113.7, 55.2, 40.1, 22.2, 19.7 ppm. GC–MS: m/z (%)
226 (96) [M]+, 211 (100), 196 (32), 165 (41), 118 (33), 105 (35), 91
(41). HRMS: calcd. for C16H18O 226.1358; found 226.1355.
1-(4-Chlorophenyl)-1-(2,4,6-trimethylphenyl)ethane (3p): 1H NMR
(300 MHz, CDCl3): δ = 7.16 (d, J = 7.6 Hz, 2 H), 7.00 (d, J =
7.6 Hz, 2 H), 6.74 (s, 2 H), 4.49 (q, J = 7.2 Hz, 1 H), 2.18 (s, 3 H),
2.01 (s, 6 H), 1.55 (d, J = 7.2 Hz, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 144.1, 139.6, 136.5, 135.7, 131.1, 130.2, 128.8, 128.2,
37.5, 21.2, 20.8, 17.0 ppm. GC–MS: m/z (%) 274 (45) [M]+, 259
(56), 179 (25), 165 (24), 125 (100), 91 (13), 77 (16). HRMS: calcd.
for C17H19ClO 258.1175; found 258.1173.
1-(2-Methoxyphenyl)-1-(2-methylphenyl)ethane (3jЈ): 1H NMR
(300 MHz, CDCl3): δ = 7.27– 6.82 (m, 8 H), 4.68 (q, J = 6.9 Hz, 1
H), 3.80 (s, 3 H), 2.21 (s, 3 H), 1.52 (d, J = 6.9 Hz, 3 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 156.8, 144.7, 136.3, 134.8, 130.1,
127.5 (2C), 126.9, 126.5, 125.7, 120.5, 110.3, 55.5, 33.8, 20.6,
19.3 ppm. GC–MS: m/z (%) 226 (74) [M]+, 211 (74), 178 (18), 165
(36), 135 (19), 105 (100), 91 (29).
1-(2,4-Dimethylphenyl)-1-phenylethane (3q): 1H NMR (300 MHz,
CDCl3): δ = 7.30–6.90 (m, 8 H), 4.27 (q, J = 7.2 Hz, 1 H), 2.28 (s,
3 H), 2.19 (s, 3 H), 1.58 (d, J = 7.2 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 146.4, 140.9, 135.9, 135.4, 131.2, 128.5,
128.3, 127.6, 126.6, 125.7, 40.6, 22.2, 20.9, 19.6 ppm. GC–MS:
m/z (%) 210 (98) [M]+, 195 (100), 180 (78), 165 (77), 115 (27), 91
(27), 77 (40).
1-(4-Ethoxyphenyl)-1-(2-methylphenyl)ethane (3k): 1H NMR
(300 MHz, CDCl3): δ = 7.30–7.10 (m, 4 H), 7.03 (d, J = 8.6 Hz, 2
H), 6.77 (d, J = 8.6 Hz, 2 H), 4.26 (q, J = 7.2 Hz, 1 H), 3.95 (q, J
= 6.9 Hz, 2 H), 2.22 (s, 3 H), 1.56 (d, J = 7.2 Hz, 3 H), 1.36 (t, J
= 6.9 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 157.0, 144.3,
138.2, 136.0, 130.4, 128.5 (2 C), 126.5, 126.0, 114.2, 63.3, 40.1, 22.2,
19.7, 14.9 ppm. GC–MS: m/z (%) 240 (39) [M]+, 225 (100), 197
(33), 182 (12), 165 (17), 115 (11), 91 (14). HRMS: calcd. for
C17H20O 240.1514;, found 240.1509.
1-(2-Ethoxyphenyl)-1-(2-methylphenyl)ethane (3kЈ): 1H NMR
(300 MHz, CDCl3): δ = 7.20–6.80 (m, 8 H), 4.68 (q, J = 7.2 Hz, 1
H), 3.96 (q, J = 6.9 Hz, 2 H), 2.26 (s, 3 H), 1.51 (d, J = 7.2 Hz, 3
H), 1.32 (t, J = 6.9 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ
= 156.2, 144.7, 136.1, 134.8, 130.0, 127.5, 126.8, 126.5, 125.7, 125.6,
120.2, 111.1, 63.3, 33.9, 20.5, 19.3, 14.8 ppm. GC–MS: m/z (%) 240
(52) [M]+, 225 (11), 211 (35), 165 (30), 119 (100), 107 (22), 91 (33).
1-(4-Chlorophenyl)-1-(2,4-dimethylphenyl)ethane (3r): 1H NMR
(300 MHz, CDCl3): δ = 7.20–6.98 (m, 6 H), 6.95 (s, 1 H), 4.22 (q,
J = 7.2 Hz, 1 H), 2.28 (s, 3 H), 2.16 (s, 3 H), 1.55 (d, J = 7.2 Hz,
3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 145.0, 140.3, 135.8,
135.7, 131.3, 128.9, 128.6, 128.4, 126.7, 126.4, 40.1, 22.1, 20.9,
19.6 ppm. GC–MS: m/z (%) 244 (34) [M]+, 229 (100), 194 (28), 179
(41), 165 (14), 115 (11), 91 (8), 77 (14). HRMS: calcd. for C16H17Cl
244.1019; found 244.1020.
1-(4-Chlorophenyl)-1-(3,4-dimethylphenyl)ethane (3s): 1H NMR
(300 MHz, CDCl3): δ = 7.30–6.90 (m, 7 H), 4.04 (q, J = 7.2 Hz, 1
H), 2.21 (s, 6 H), 1.58 (d, J = 7.2 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 145.2, 143.3, 136.5, 134.4, 131.6, 129.7,
128.9, 128.8, 128.4, 124.8, 43.8, 21.0, 19.8, 19.3 ppm. GC–MS
m/z (%) 244 (34) [M]+, 229 (100), 194 (27), 165 (15), 103 (12), 91
(11), 77 (14).
1-(2,5-Dimethoxy)-1-phenylethane (3t): 1H NMR (300 MHz,
CDCl3): δ = 7.24–7.13 (m, 5 H), 6.76–6.64 (m, 3 H), 4.54 (q, J =
7.2 Hz, 1 H), 3.70 (s, 3 H), 3,68 (s, 3 H), 1.55 (d, J = 7.2 Hz, 3
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 153.6, 151.2, 126.1,
136.3, 128.1, 127.6, 125.7, 114.7, 110.6, 110.4, 56.1, 55.5, 37.5,
20.9 ppm. GC–MS: m/z (%) 242 (100) [M]+, 227 (40), 211 (9), 165
(13), 103 (13), 91 (71).
1-(4,6-Dimethyl-2-methoxyphenyl)-1-phenylethane (3l): 1H NMR
(300 MHz, CDCl3): δ = 7.30–7.10 (m, 5 H), 6.60 (s, 1 H), 6.55 (s,
1 H), 4.65 (q, J = 7.2 Hz, 1 H), 3.59 (s, 3 H), 2.29 (s, 3 H), 2.18 (s,
3 H), 1.64 (d, J = 7.2 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 158.0, 146.0, 137.2, 136.5, 130.5, 127.7, 127.0, 125.0, 124.2,
110.7, 55.5, 35.8, 21.3, 20.6, 17.3 ppm. GC–MS: m/z (%) 240 (98)
[M]+, 225 (99), 178 (31), 165 (58), 115 (24), 91 (100), 77 (31).
HRMS: calcd. for C17H20O 240.1514; found 240.1511.
1-(4-Chlorophenyl)-1-(2,5-dimethoxyphenyl)ethane (3u): 1H NMR
(300 MHz, CDCl3): δ = 7.19 (d, J = 8.4 Hz, 2 H), 7.15 (d, J =
8.4 Hz, 2 H), 6.76–6.66 (m, 3 H), 4.48 (q, J = 7.2 Hz, 1 H), 3.72
1-(4-Chlorophenyl)-1-(2-methoxy-4,6-dimethylphenyl)ethane (3m):
1H NMR (300 MHz, CDCl3): δ = 7.17 (d, J = 8.6 Hz, 2 H), 7.11
Eur. J. Org. Chem. 2006, 4231–4236
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