Synthesis of Arylated Quinolines by Chemo- and Site-selective Suzuki–Miyaura Reactions
1,4-dioxane (3 mL), 4c was isolated as a white solid; yield:
86 mg (85%), mp 231–2338C. H NMR (300 MHz, CDCl3):
890, 882 (w), 829, 818, 788 (s), 755, 746, 732, 721, 701, 669,
1
648, 637 (w), 623 (m), 590, 575, 538 cmꢀ1 (w); GC-MS (EI,
70 eV): m/z (%)=525 ([M]+, 75), 524 (100), 469 (18), 468
(45); HR-MS (ESI-TOF/MS): m/z=526.3473, calcd. for
C39H43N [M+H]+: 526.3468.
d=2.09 (s, 6H, 2CH3), 2.15 (s, 6H, 2CH3), 2.32(s, 6H,
2CH3), 6.70–6.72 (m, 3H, ArH), 6.79 (br s, 3H, ArH), 7.00
(s, 1H, ArH), 7.07 (br s, 2H, ArH), 7.20 (dd, J=4.14,
8.49 Hz, 1H, ArH), 7.52 (s, 1H, ArH), 8.21 (dd, J=1.77,
8.49 Hz, 1H, ArH), 8.84 (dd, J=1.82, 4.14 Hz, 1H, ArH);
13C NMR (62.9 MHz, CDCl3): d=20.1, 20.3, 20.3 (CH3),
119.2 (CH), 124.7 (C), 126.9, 126.9, 127.3, 128.1, 128.5, 128.6,
128.6, 133.1 (CH), 135.2, 135.7, 136.9, 137.0, 137.3, 138.4,
5,7,8-Tris(4-methoxyphenyl)quinoline (4f): Starting with 2
(100 mg, 0.23 mmol), 3f (104 mg, 0.69 mmol), PdACHTUNGTRENNUNG(PPh3)4
(24 mg, 9 mol%, 0.0207 mmol), K2CO3 (2M, 1.0 mL), and
1,4-dioxane (3 mL), 4f was isolated as a white solid; yield:
1
95 mg (93%), mp 149–1518C. H NMR (300 MHz, CDCl3):
˜
138.4, 140.3, 140.4, 146.3 (C), 149.0 (CH); IR (KBr): n=
d=3.67 (s, 3H, OCH3), 3.72 (s, 3H, OCH3), 3.79 (s, 3H,
OCH3), 6.66 (d, J=8.76 Hz, 2H, ArH), 6.76 (d, J=8.73 Hz,
2H, ArH), 6.95 (d, J=8.70 Hz, 2H, ArH), 7.03 (d, J=
8.76 Hz, 2H, ArH), 7.12 (d, J=8.76 Hz, 2H, ArH), 7.20 (dd,
J=4.11, 8.19 Hz, 1H, ArH), 7.37 (d, J=8.76 Hz, 2H, ArH),
7.50 (s, 1H, ArH), 8.20 (dd, J=1.77, 8.52 Hz, 1H, ArH),
8.83 (dd, J=1.77, 4.11 Hz, 1H, ArH); 13C NMR (62.9 MHz,
CDCl3): d=55.1, 55.1, 55.4 (OCH3), 113.1, 113.3, 114.0,
120.3 (CH), 126.0 (C), 129.9 (CH), 130.5 (C), 131.2, 131.2
(CH), 131.8 (C), 133.0 (CH), 134.1 (C), 134.2 (CH), 137.3,
139.1, 141.0 147.5 (C), 150.1 (CH), 158.2, 158.2, 159.3 (C);
3025 (w), 2912, 2853 (m), 2732, 1955, 1921, 1888 (w), 1598,
1588 (s), 1556, 1538, 1501 (w), 1454 (m), 1395 (w), 1373,
1353, 1343 (m), 1300, 1291, 1260, 1222, 1189, 1165, 1157,
1088 (w), 1037 (m), 996, 982, 948, 934, 911, 903, 896, 877,
862 (w), 853, 845 (s), 822 (w), 797, 788 (s), 762, 738, 725 (m),
702, 690 (s), 657, 605, 592, 567, 558, 547, 535, 528 cmꢀ1 (w);
GC-MS (EI, 70 eV): m/z (%)=441 ([M]+, 70), 440 (100),
427 (26), 426 (75), 336 (20); HR-MS (ESI-TOF/MS): m/z=
442.2528, calcd. for C33H32N [M+H]+: 442.2529.
5,7,8-Tris(4-ethylphenyl)quinoline (4d): Starting with 2
˜
(100 mg, 0.23 mmol), 3d (103 mg, 0.69 mmol), Pd
G
IR (KBr): n=3034, 2999, 2925, 2900 (w), 2829 (m), 1607 (s),
(24 mg, 9 mol%, 0.0207 mmol), K2CO3 (2M, 1.0 mL), and
1574, 1554 (w), 1509 (s), 1491, 1460, 1450, 1439 (m), 1410,
1392, 1348, 1338, 1304 (w), 1288, 1238, 1173, 1107, 1028 (s),
974 (m), 954, 933, 903, 880 (w), 826, 819, 802, 795 (s), 736,
713, 702, 675, 654, 643, 624 (w), 573, 553, 538 cmꢀ1 (w); GC-
MS (EI, 70 eV): m/z (%)=447 ([M]+, 70), 432 (9), 340 (13);
HR-MS (ESI-TOF/MS): m/z=448.1905, calcd. for
C30H26NO3 [M+H]+: 448.1907.
5,7,8-Tris(4-fluorophenyl)quinoline (4g): Starting with 2
(100 mg, 0.23 mmol), 3g (96 mg, 0.69 mmol), PdACHTUNGTRENNUNG(PPh3)4
(24 mg, 9 mol%, 0.0207 mmol), K2CO3 (2m, 1.0 mL), and
1,4-dioxane (3 mL), 4d was isolated as a yellow oil; yield:
1
91 mg (90%). H NMR (300 MHz, CDCl3): d=1.10 (t, J=
7.56 Hz, 3H, CH3), 1.16 (t, J=7.56 Hz, 3H, CH3), 1.23 (t,
J=7.56 Hz, 3H, CH3), 2.46–2.70 (m, 6H, 3CH2), 6.93 (d, J=
8.40 Hz, 2H, ArH), 7.00–7.04 (m, 4H, ArH), 7.09–7.13 (m,
2H, ArH), 7.20 (dd, J=4.11, 8.49 Hz, 1H, ArH), 7.23 (d,
J=8.28 Hz, 2H, ArH), 7.36 (d, J=8.16 Hz, 2H, ArH), 7.54
(s, 1H, ArH), 8.23 (dd, J=1.83, 8.52 Hz, 1H, ArH), 8.82
(dd, J=1.83, 4.14 Hz, 1H, ArH); 13C NMR (75.4 MHz,
CDCl3): d=15.2, 15.3, 15.6 (3CH3), 28.4, 28.6, 28.6 (3CH2),
120.3 (CH), 126.0 (C), 127.0, 127.2, 128.0, 130.0, 130.0, 130.1,
131.8, 134.3 (CH), 135.4, 136.7, 137.9, 138.9, 139.5, 141.4,
1,4-dioxane (3 mL), 4g was isolated as a white solid; yield:
1
74 mg (79%), mp 222–2248C. H NMR (300 MHz, CDCl3):
d=6.79–6,94 (m, 4H, ArH), 7.02–7.07 (m, 2H, ArH), 7.10–
7.16 (m, 4H, ArH), 7.28 (dd, J=4.14, 8.49 Hz, 1H, ArH),
7.41 (m, 2H, ArH), 7.47 (s, 1H, ArH), 8.15 (dd, J=1.77,
8.52 Hz, 1H, ArH), 8.83 (dd, J=1.77, 4.11 Hz, 1H, ArH).
13C NMR (62.9 MHz, CDCl3): d=114 (d, J=21.4 Hz), 115.0
(d, J=21.4 Hz), 115.6 (d, J=21.4 Hz), 120.9 (CH), 126.1
(C), 129.6, 131.5 (d, J=1.7 Hz), 131.7 (d, J=1.7 Hz), 133.3,
133.5 (CH), 133.6 (d, J=3.5 Hz) (C), 134.0 (CH), 135.0 (d,
J=3.5 Hz), 137.1 (d, J=3.5 Hz), 137.4, 138.9, 140.5, 147.1
(C), 150.4 (CH), 161.7 (d, J=246.9 Hz) (CF), 161.8 (d, J=
246.0 Hz) (CF), 162.6 (d, J=247.4 Hz) (CF); 19F NMR
˜
142.2, 142.4, 143.7, 147.4 (C), 150.1 (CH); IR (KBr): n=
3127, 3046, 3023 (w), 2961, 2929, 2870 (m), 1903, 1792, 1716,
1670, 1634, 1611 (w), 1591 (m), 1570 (w), 1512 (m), 1491
(w), 1453, 1446 (m), 1410, 1392, 1373, 1349, 1336, 1303,
1280, 1256, 1183, 1154, 1115, 1097, 1060, 1048, 1020 (w), 977
(m), 902, 880 (w), 827 (s), 792 (m), 732, 698, 668, 652, 630,
608, 570 cmꢀ1 (w); GC-MS (EI, 70 eV): m/z (%)=441
([M]+, 61), 440 (100), 412 (28), 336 (15); HR-MS (ESI-TOF/
MS): m/z=442.2524, calcd. for C33H32N [M+H]+: 442.2529.
5,7,8-Tris(4-tert-butylphenyl)quinoline (4e): Starting with
˜
2 (100 mg, 0.23 mmol), 3e (122 mg, 0.69 mmol), Pd
(24 mg, 9 mol%, 0.0207 mmol), K2CO3 (2M, 1.0 mL), and
(PPh3)4
(282.4 MHz): d=ꢀ144.1, ꢀ115.5, ꢀ155.3; IR (KBr): n=
3038, 2929, 2859, 1892 (w), 1604 (m), 1558 (w), 1507 (s),
1490 (m), 1448, 1404, 1390, 1351, 1337, 1295 (w), 1218, 1156
(s), 1094, 1087 (m), 1038 (w), 1014, 976 (m), 956, 939, 907,
899, 882 (w), 827, 815, 797 (s), 734 (m), 725, 713, 695, 669,
655, 644, 621 (w), 603, 560, 536 cmꢀ1 (m); GC-MS (EI,
70 eV): m/z (%)=411 ([M]+, 44), 410 (100); HR-MS (EST-
TOF/MS): m/z=412.1301, calcd. for. C27H17F3N [M+H]+:
412.1308.
5,7,8-Tris(4-chlorophenyl)quinoline (4h): Starting with 2
(100 mg, 0.23 mmol), 3h (108 mg, 0.69 mmol), PdACHTUNGTRENNUNG(PPh3)4
(24 mg, 9 mol%, 0.0207 mmol), K2CO3 (2M, 1.0 mL), and
1,4-dioxane (3 mL), 4h was isolated as a white solid; yield:
1,4-dioxane (3 mL), 4e was isolated as a white solid; yield:
1
100 mg (83%), mp 245–2478C. H NMR (300 MHz, CDCl3):
d=1.15 (s, 9H, 3CH3), 1.21 (s, 9H, 3CH3), 1.30 (s, 9H,
3CH3), 6.97 (d, J=8.55 Hz, 2H, ArH), 7.04–7.10 (m, 4H,
ArH), 7.19–7.21 (m, 3H, ArH), 7.35–7.44 (m, 4H, ArH),
7.57 (s, 1H, ArH), 8.25 (dd, J=1.80, 8.52 Hz, 1H, ArH),
8.83 (dd, J=1.80, 4.14 Hz, 1H, ArH); 13C NMR (75.4 MHz,
CDCl3): d=31.2, 31.4, 31.4 (9CH3), 34.3, 34.4, 34.6 (C),
120.3, 124.3, 124.4, 125.4 (CH), 125.9 (C), 129.7, 129.8 (CH),
130.4, 131.6, 134.4 (CH), 135.3, 136.5, 136.5, 138.0, 138.6,
139.4, 141.7, 147.2, 149.0, 149.2 (C), 150.6 (CH); IR (KBr):
1
˜
n=3030 (w), 2955, 2901, 2865 (m), 1906, 1714, 1673, 1651,
84 mg (80%), mp 223–2258C. H NMR (300 MHz, CDCl3):
1633, 1609, 1593, 1567, 1557 (w), 1510 (m), 1489 (w), 1461,
1445, 1391, 1361 (m), 1309 (w), 1268 (m), 1309 (w), 1268
(m), 1200, 1165, 1118, 1101, 1101, 1018, 977, 947, 923, 908,
d=7.00 (d, J=8.58 Hz, 2H, ArH), 7.09–7.12 (m, 4H, ArH),
7,20 (d, J=8.52 Hz, 2H, ArH), 7.28 (dd, J=4.14, 8.52 Hz,
1H, ArH), 7.35–7.40 (m, 4H, ArH), 7.45 (s, 1H, ArH), 8.15
Adv. Synth. Catal. 2011, 353, 2761 – 2774
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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