5360
A. Arcadi et al. / Tetrahedron 64 (2008) 5354–5361
CDCl3): d 8.53 (s, 1H), 8.33 (d, J¼8.4 Hz, 2H), 8.08 (d, J¼8.7 Hz, 1H),
7.91 (s, 1H), 7.81 (d, J¼8.4 Hz, 2H), 7.66 (dd, J1¼8.8 Hz, J2¼1.6 Hz,
9H). 13C NMR (50.3 MHz, CDCl3): 158.4, 148.3, 148.1, 138.7, 137.6,
130.7, 129.8, 129.5, 129.1, 128.5, 128.2, 125.7, 125.6, 125.4, 118.3,
43.8, 32.2, 27.8, 27.5, 27.2, 24.2. IR (KBr): 3020, 2890, 1600,
1540 cmꢁ1. MS (EI) m/z: 341 (Mþ, 40), 327 (16), 285 (100). Anal.
Calcd for C25H27N: C, 87.93; H, 7.97; N, 4.10. Found: C, 87.67; H,
7.99; N, 4.12.
1H), 7.45 (d, J¼8.4 Hz, 2H), 7.40 (d, J¼8.4 Hz, 2H), 2.50 (s, 3H). 13
C
NMR (50.3 MHz, CDCl3): 155.8, 150.1, 148.0, 143.0, 139.2, 134.3,
132.7, 129.7, 129.4, 128.1, 127.3, 123.9 (q, J¼272 Hz), 122.5 (q,
J¼2.7 Hz), 120.4, 118.6, 116.2, 113.4, 30.2. IR (KBr): 3010, 2200,
1580 cmꢁ1. MS (EI) m/z: 388 (Mþ, 100), 374 (31). Anal. Calcd for
C
7.22.
24H15 F3N2: C, 74.22; H, 3.89; N, 7.21. Found: C, 73.99; H, 3.90; N,
4.4. Representative procedure for the sequential
hydroarylation/cycloamination of 1 with aryltrifluoroborate
salts. Synthesis of 2-(4-methoxyphenyl)-4-(4-methyl-
phenyl)quinoline 4a
4.3.5. 1-{3-[2-(4-Chlorophenyl)quinolin-4-yl]phenyl}ethanone 4k
Off-white solid (127 mg) was obtained from 120 mg of 1f and
230 mg of 2f (76% yield). Mp 117–119 ꢀC. 1H NMR (200 MHz,
CDCl3): d 8.23 (d, J¼8.4 Hz, 1H), 8.12 (d, J¼8.5 Hz, 2H), 8.16–8.08
(m, 2H), 7.82–7.61 (m, 4H), 7.77 (s, 1H), 7.47 (d, J¼8.5 Hz, 2H),
7.51–7.45 (m, 1H), 2.66 (s, 3H). 13C NMR (50.3 MHz, CDCl3): 197.7,
155.5, 148.7, 148.2, 138.7, 137.7, 137.5, 135.7, 134.0, 130.2, 129.9,
129.2, 129.0, 128.8, 128.4, 126.9, 125.5, 125.2, 118.9, 26.8. IR (KBr):
3020, 1680, 1590 cmꢁ1. MS (EI) m/z: 359 (Mþþ2, 35), 357 (Mþ,
100), 317 (24), 315 (65). Anal. Calcd for C23H16 ClNO: C, 77.20; H,
4.51; N, 3.91. Found: C, 76.94; H, 4.50; N, 3.92.
To a solution of 3-(2-aminophenyl)-1-(4-methoxyphenyl) prop-
2-yn-1-one 1a (0.128 g, 0.51 mmol) in ethanol (4 mL) were added
potassium 4-methylphenyltrifluoroborate 3a (0.303 g, 1.53 mmol),
acetic acid (4.5 mL, 0.075 mmol), Pd(OAc)2 (0.006 g, 0.027 mmol)
and 1,2-bis(diphenylphosphino)ethane (0.011 g, 0.027 mmol). The
mixture was stirred at 80 ꢀC for 8 h under nitrogen atmosphere. Af-
ter cooling, the mixture was purified by column chromatography
(silica gel; hexane–ethyl acetate 97:3 v/v) to give 4a (0.149 g, 90%
yield).
4.3.6. 2-(4-Chlorophenyl)-4-(4-fluorophenyl)quinoline 4l
Acknowledgements
White solid (121 mg) was obtained from 120 mg of 1f and
197 mg of 2e (77% yield). Mp 92–94 ꢀC. 1H NMR (200 MHz,
CDCl3): d 8.21 (d, J¼8.4 Hz, 1H), 8.11 (d, J¼8.5 Hz, 2H), 7.83 (d,
J¼8.4 Hz, 1H), 7.70 (s, 1H), 7.76–7.69 (m, 1H), 7.46 (d, J¼8.5 Hz,
2H), 7.53–7.45 (m, 3H), 7.22 (m, 2H). 13C NMR (50.3 MHz, CDCl3):
162.9 (d, J¼248 Hz), 155.4, 148.5 (d, J¼23 Hz), 137.8, 135.6, 134.1,
131.3, 130.1, 129.8, 129.0, 128.8, 128.5, 126.7, 125.7, 125.4, 118.9,
115.7 (d, J¼22 Hz). IR (KBr): 3020, 1600, 1540 cmꢁ1. MS (EI) m/z:
335 (Mþþ2, 36), 333 (Mþ, 100). Anal. Calcd for C21H13ClFN: C,
75.56; H, 3.93; N, 4.20. Found: C, 75.40; H, 3.95; N, 4.21.
`
This work was financed by the Ministero dell’Universita e della
Ricerca, Rome, and by the University of L’Aquila.
Supplementary data
Details of the computational study. Supplementary data associ-
ated with this article can be found in the online version, at
4.3.7. 1-{4-[4-(1-Naphthyl)quinolin-2-yl]phenyl}ethanone 4m
Pale brown solid (129 mg) was obtained from 130 mg of 1g and
255 mg of 2c (70% yield). Mp 158–160 ꢀC. 1H NMR (200 MHz,
CDCl3): d 8.30 (d, J¼8.3 Hz, 2H), 8.32–8.25 (m, 1H), 8.07 (d,
J¼8.3 Hz, 2H), 8.02–7.92 (m, 2H), 7.93 (s, 1H), 7.75–7.25 (m, 8H),
2.63 (s, 3H). 13C NMR (50.3 MHz, CDCl3): 197.8, 155.4, 148.5, 148.3,
143.6, 137.4, 135.7, 133.5, 131.9, 130.1, 129.9, 128.9, 128.8, 128.4,
127.7, 127.4, 127.3, 126.9, 126.6, 126.2, 125.9, 125.3, 120.4, 26.8. IR
(KBr): 3020, 1680, 1600 cmꢁ1. MS (EI) m/z: 373 (Mþ, 100), 359
(35). Anal. Calcd for C27H19NO: C, 86.84; H, 5.13; N, 3.75. Found:
C, 87.05; H, 5.11; N, 3.75.
References and notes
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4.3.8. 2-(4-tert-Butyl-cyclohex-1-enyl)-4-(4-methylsulfanyl-phenyl)-
quinoline 4n
Orange solid (86 mg) was obtained from 84 mg of 1h and
150 mg of 2d (74% yield). Mp 60–62 ꢀC. 1H NMR (200 MHz,
CDCl3): d 8.11 (d, J¼8.4 Hz, 1H), 7.83 (d, J¼8.3 Hz, 1H), 7.65 (t,
J¼7.1 Hz, 1H), 7.47 (s, 1H), 7.45–7.35 (m, 5H), 6.79 (t, J¼2.5 Hz,
1H), 3.05–2.90 (m, 1H), 2.55 (s, 3H), 2.55–2.00 (m, 4H), 1.45–1.25
(m, 2H), 0.93 (s, 9H). 13C NMR (50.3 MHz, CDCl3): 158.5, 148.4,
147.5, 139.0, 137.6, 135.3, 130.6, 129.9, 129.1, 126.3, 125.7, 125.5,
125.3, 118.2, 43.9, 32.2, 27.8, 27.5, 27.2, 24.2, 15.7. IR (KBr): 3020,
2970, 1600, 1590 cmꢁ1. MS (EI) m/z: 388 (Mþ, 51), 373 (15), 331
(100). Anal. Calcd for C26H29NS: C, 80.57; H, 7.54; N, 3.61. Found:
C, 80.83; H, 7.56; N, 3.61.
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4.3.9. 2-(4-tert-Butyl-cyclohex-1-enyl)-4-phenyl-quinoline 4o
Yellow solid (60 mg) was obtained from 83 mg of 1h and 163 mg
of 3b (60% yield). Mp 41–42 ꢀC. 1H NMR (200 MHz, CDCl3): d 8.12 (d,
J¼8.4 Hz, 1H), 7.82 (d, J¼7.9 Hz, 1H), 7.65 (dt, J1¼7.5 Hz, J2¼1.2 Hz,
1H), 7.50–7.35 (m, 7H), 6.79 (t, J¼2.7 Hz, 1H), 3.05–2.90 (m, 1H),
2.60–2.30 (m, 2H), 2.15–2.00 (m, 2H), 1.45–1.20 (m, 2H), 0.93 (s,