F. Berthiol et al. / Tetrahedron 62 (2006) 4372–4383
4379
3.2.7. 1-(4-Cyanophenyl)-2-methylpentan-3-one (7b)
(Table 1, entry 19). From 4-bromobenzonitrile (0.182 g,
1 mmol), 2-methylpent-1-en-3-ol (0.120 g, 1.2 mmol),
NaHCO3 (0.168 g, 2 mmol) and Pd complex (10 mmol),
MS (70 eV); m/z (%) 227 (MC%, 100); C15H17NO: calcd C
79.26, H 7.54; Found C 79.35, H 7.46. Before purification
1
10a was also observed H NMR (300 MHz, CDCl3) d 1.18
(t, JZ7.3 Hz, 3H).
1
product 7b was obtained in 90% (0.181 g) yield. H NMR
(300 MHz, CDCl3) d 7.55 (d, JZ8.1 Hz, 2H), 7.24 (d, JZ
8.1 Hz, 2H), 3.04 (dd, JZ13.4, 7.5 Hz, 1H), 2.81 (sext., JZ
7.1 Hz, 1H), 2.61 (dd, JZ13.4, 6.8 Hz, 1H), 2.47 (dq, JZ
17.8, 7.3 Hz, 1H), 2.23 (dq, JZ17.8, 7.3 Hz, 1H), 1.09 (d,
JZ6.9 Hz, 3H), 0.96 (t, JZ7.3 Hz, 3H); 13C NMR
(75 MHz, CDCl3) d 213.5, 145.5, 132.0, 129.6, 118.7,
109.9, 47.2, 38.7, 34.8, 16.7, 7.4; C13H15NO: calcd C 77.58,
H 7.51; Found C 77.32, H 7.72. Before purification 7a was
3.2.11. 3-(4-tert-Butylphenyl)-2-methyl-1-phenylpropan-
1-one (11) (Table 2, entry 1). From 4-tert-butylbromo-
benzene (0.213 g, 1 mmol), 2-methyl-3-phenylprop-1-en-3-
ol (0.178 g, 1.2 mmol), K2CO3 (0.276 g, 2 mmol) and Pd
complex (1 mmol), product 11 was obtained in 38%
(0.107 g) yield. 1H NMR (300 MHz, CDCl3) d 7.91 (d,
JZ7.4 Hz, 2H), 7.52 (t, JZ7.4 Hz, 1H), 7.42 (t, JZ7.4 Hz,
2H), 7.29 (d, JZ8.4 Hz, 2H), 7.11 (d, JZ8.4 Hz, 2H), 3.73
(sext., JZ7.0 Hz, 1H), 3.13 (dd, JZ13.8, 6.1 Hz, 1H), 2.65
(dd, JZ13.8, 7.9 Hz, 1H), 1.28 (s, 9H), 1.20 (d, JZ6.9 Hz,
3H); 13C NMR (75 MHz, CDCl3) d 203.9, 149.0, 136.8,
136.5, 132.8, 128.7, 128.6, 128.3, 125.2, 42.7, 38.8, 34.3,
31.4, 17.4; MS (70 eV); m/z (%) 280 (MC%, 58); C20H24O:
calcd C 85.67, H 8.63; Found C 85.59, H 8.66.
1
also observed H NMR (300 MHz, CDCl3) d 1.10 (t, JZ
7.3 Hz, 3H).
3.2.8. 2-Methyl-1-(o-tolyl)pentan-3-one (8b) (Table 1,
entry 23). From 2-methylbromobenzene (0.171 g,
10 mmol), 2-methylpent-1-en-3-ol (0.120 g, 1.2 mmol),
NaHCO3 (0.168 g, 2 mmol) and Pd complex (10 mmol),
1
product 8b was obtained in 93% (0.177 g) yield. H NMR
3.2.12. 3-(4-Methoxyphenyl)-2-methyl-1-phenylpropan-
1-one (12) (Table 2, entry 4). From 4-bromoanisole
(0.187 g, 1 mmol), 2-methyl-3-phenylprop-1-en-3-ol
(0.178 g, 1.2 mmol), K2CO3 (0.276 g, 2 mmol) and Pd
complex (1 mmol), product 12 was obtained in 40%
(0.102 g) yield. 1H NMR (300 MHz, CDCl3) d 7.92 (d,
JZ7.4 Hz, 2H), 7.54 (t, JZ7.4 Hz, 1H), 7.44 (t, JZ7.4 Hz,
2H), 7.10 (d, JZ8.6 Hz, 2H), 6.80 (d, JZ8.6 Hz, 2H), 3.76
(s, 3H), 3.70 (sext., JZ7.1 Hz, 1H), 3.13 (dd, JZ13.8,
6.6 Hz, 1H), 2.63 (dd, JZ13.8, 7.7 Hz, 1H), 1.19 (d, JZ
7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3) d 203.9, 158.0,
136.5, 132.9, 132.0, 130.0, 128.6, 128.3, 113.8, 55.2, 43.0,
38.5, 17.3; MS (70 eV); m/z (%) 254 (MC%, 40).
(300 MHz, CDCl3) d 7.13–7.05 (m, 4H), 2.96 (dd, JZ13.4,
7.0 Hz, 1H), 2.83 (sext., JZ7.0 Hz, 1H), 2.56 (dd, JZ13.5,
7.3 Hz, 1H), 2.42 (dq, JZ17.9, 7.3 Hz, 1H), 2.31 (s, 3H),
2.23 (dq, JZ17.9, 7.3 Hz, 1H), 1.09 (d, JZ6.7 Hz, 3H),
0.96 (t, JZ7.3 Hz, 3H); 13C NMR (75 MHz, CDCl3) d
214.9, 138.0, 136.0, 130.4, 129.7, 126.3, 125.9, 46.4, 36.5,
35.3, 19.4, 16.6, 7.6; MS (70 eV); m/z (%) 190 (MC%, 15);
C13H18O: calcd C 82.06, H 9.53; Found C 82.01, H 9.72.
Before purification 8a was also observed 1H NMR
(300 MHz, CDCl3) d 1.15 (t, JZ7.3 Hz, 3H).
3.2.9. 2-Methyl-1-(3-pyridinyl)pentan-3-one (9b)
(Table 1, entry 27). From 3-bromopyridine (0.158 g,
1 mmol), 2-methylpent-1-en-3-ol (0.120 g, 1.2 mmol),
NaHCO3 (0.168 g, 2 mmol) and Pd complex (10 mmol),
3.2.13. 3-[4-(Dimethylamino)phenyl]-2-methyl-1-phenyl-
propan-1-one (13) (Table 2, entry 6). From 4-bromo-N,N-
dimethylaniline (0.200 g, 1 mmol), 2-methyl-3-phenylprop-
1-en-3-ol (0.178 g, 1.2 mmol), K2CO3 (0.276 g, 2 mmol)
and Pd complex (1 mmol), product 13 was obtained in 23%
(0.062 g) yield. 1H NMR (300 MHz, CDCl3) d 7.92 (d, JZ
7.4 Hz, 2H), 7.54 (t, JZ7.4 Hz, 1H), 7.44 (t, JZ7.4 Hz,
2H), 7.08 (d, JZ8.7 Hz, 2H), 6.68 (d, JZ8.7 Hz, 2H), 3.70
(sext., JZ7.0 Hz, 1H), 3.07 (dd, JZ13.9, 5.9 Hz, 1H), 2.90
(s, 6H), 2.59 (dd, JZ13.8, 8.0 Hz, 1H), 1.19 (d, JZ6.9 Hz,
3H); 13C NMR (75 MHz, CDCl3) d 204.1, 158.0, 136.6,
129.7, 128.6, 128.3, 127.6, 126.4, 112.9, 43.0, 40.8, 38.4,
17.1; MS (70 eV); m/z (%) 267 (MC%, 40); C18H21NO: calcd
C 80.86, H 7.92; Found C 80.78, H 8.05.
1
product 9b was obtained in 80% (0.142 g) yield. H NMR
(300 MHz, CDCl3) d 8.39 (dd, JZ4.8, 1.6 Hz, 1H), 8.37 (d,
JZ2.0 Hz, 1H), 7.41 (dt, JZ7.8, 2.0 Hz, 1H), 7.14 (ddd,
JZ7.8, 4.8, 0.7 Hz, 1H), 2.96 (dd, JZ13.5, 7.3 Hz, 1H),
2.78 (sext., JZ7.0 Hz, 1H), 2.56 (dd, JZ13.5, 7.0 Hz, 1H),
2.43 (dq, JZ17.9, 7.3 Hz, 1H), 2.22 (dq, JZ17.9, 7.3 Hz,
1H), 1.06 (d, JZ6.9 Hz, 3H), 0.93 (t, JZ7.3 Hz, 3H); 13C
NMR (75 MHz, CDCl3) d 213.8, 150.2, 147.6, 136.4, 135.2,
123.2, 47.4, 35.9, 35.0, 16.7, 7.5; C11H15NO: calcd C 74.54,
H 8.53; Found C 74.72, H 8.38. Before purification 9a was
1
also observed H NMR (300 MHz, CDCl3) d 1.14 (t, JZ
7.3 Hz, 3H).
3.2.10. 2-Methyl-1-(3-quinolyl)pentan-3-one (10b)
(Table 1, entry 31). From 3-bromoquinoline (0.136 mL,
1 mmol), 2-methylpent-1-en-3-ol (0.120 g, 1.2 mmol),
NaHCO3 (0.168 g, 2 mmol) and Pd complex (10 mmol),
product 10b was obtained in 97% (0.220 g) yield. 1H NMR
(300 MHz, CDCl3) d 8.74 (d, JZ1.8 Hz, 1H), 8.07 (d, JZ
8.6 Hz, 1H), 7.90 (d, JZ1.8 Hz, 1H), 7.75 (dd, JZ8.2,
1.0 Hz, 1H), 7.65 (td, JZ8.2, 1.4 Hz, 1H), 7.51 (td, JZ8.1,
1.1 Hz, 1H), 3.18 (dd, JZ13.7, 7.4 Hz, 1H), 2.93 (sext., JZ
7.1 Hz, 1H), 2.74 (dd, JZ13.7, 6.9 Hz, 1H), 2.50 (dq, JZ
17.8, 7.3 Hz, 1H), 2.26 (dq, JZ17.8, 7.3 Hz, 1H), 1.15 (d,
JZ6.9 Hz, 3H), 0.96 (t, JZ7.3 Hz, 3H); 13C NMR
(75 MHz, CDCl3) d 213.8, 151.8, 146.7, 135.4, 132.6,
129.0, 128.9, 128.0, 127.4, 126.8, 47.5, 36.1, 35.1, 16.9, 7.6;
3.2.14. 3-(4-Fluorophenyl)-2-methyl-1-phenylpropan-1-
one (14) (Table 2, entry 11). From 4-fluorobromobenzene
(0.175 g, 1 mmol), 2-methyl-3-phenylprop-1-en-3-ol
(0.178 g, 1.2 mmol), NaHCO3 (0.168 g, 2 mmol) and Pd
complex (1 mmol), product 14 was obtained in 88%
(0.213 g) yield. 1H NMR (300 MHz, CDCl3) d 7.89 (d,
JZ7.4 Hz, 2H), 7.54 (t, JZ7.4 Hz, 1H), 7.43 (t, JZ7.4 Hz,
2H), 7.14 (dd, JZ8.7, 5.3 Hz, 2H), 6.93 (d, JZ8.8 Hz, 2H),
3.71 (sext., JZ6.9 Hz, 1H), 3.13 (dd, JZ13.8, 6.8 Hz, 1H),
2.67 (dd, JZ13.8, 7.9 Hz, 1H), 1.19 (d, JZ6.9 Hz, 3H); 13C
NMR (75 MHz, CDCl3) d 203.5, 161.4 (d, JC–FZ243.8 Hz),
4
3
136.4, 135.5 (d, JC–FZ2.9 Hz), 133.0, 130.5 (d, JC–F
Z
8.0 Hz), 128.6, 128.2, 115.1 (d, 2JC–FZ21.3 Hz), 42.8, 38.5,