Z. Bao et al. / Tetrahedron xxx (xxxx) xxx
5
133.7, 132.7, 130.2, 129.4, 129.2, 128.5, 128.3, 125.9, 121.4, 120.2,
113.8, 20.9.
2H), 7.28e7.20 (m, 3H), 7.06e7.04 (m, 1H), 7.00e6.95 (m, 1H), 3.76
(s, 3H), 2.45 (s, 3H). 13C NMR (125 MHz, CDCl3)
161.9, 159.7, 152.7,
148.8, 140.2, 136.1, 131.7, 129.8, 129.0, 128.7, 128.4, 126.2, 126.1,
125.8, 124.2, 115.5, 42.3, 21.4. IR (neat) 2989, 2903, 1611, 1564,
d
4.2.1.14. Compound 4n [9]: pale yellow solid. 1H NMR (500 MHz,
n
CDCl3, TMS)
d
8.44 (d, J ¼ 8.5 Hz, 2H), 7.97 (d, J ¼ 9.5 Hz,1H), 7.85 (d,
1539, 1482, 1442, 1389, 1356, 1288, 1170, 1074, 927, 837, 766,
698 cmꢁ1. HRMS (ESI) Calcd for C22H20N3 [M þ Hþ] 326.1652, found
326.1664.
J ¼ 10.0 Hz, 1H), 7.78e7.76 (m, 3H), 7.49 (t, J ¼ 9.5 Hz, 1H), 7.41 (br,
1H), 7.31e7.26 (m, 4H), 2.43 (s, 3H), 2.40 (s, 3H). 13C NMR (125 MHz,
CDCl3)
d 160.5, 157.3, 151.1, 140.3, 136.1, 136.0, 133.6, 132.7, 129.4,
129.2, 129.1, 128.5, 125.7, 121.3, 120.2, 113.8, 21.5, 20.9.
4.2.1.21. Compound 4u: white solid. m.p. 132.7e133.4 ꢀC. 1H NMR
(400 MHz, CDCl3, TMS)
d
8.91 (d, J ¼ 8.4, 6.8 Hz, 1H), 8.16 (s, 2H),
4.2.1.15. Compound 4o [8]: yellow solid. 1H NMR (400 MHz, CDCl3,
8.01 (d, J ¼ 8.0 Hz, 1H), 7.88 (d, J ¼ 8.0 Hz, 1H), 7.81 (td, J ¼ 8.4,
1.2 Hz, 1H), 7.72 (br, 1H), 7.54 (td, J ¼ 8.0, 0.8 Hz, 1H), 7.29e7.10 (m,
TMS)
d
8.41 (d, J ¼ 8.0 Hz, 2H), 7.96 (d, J ¼ 8.0 Hz, 1H), 7.84 (d,
J ¼ 9.2 Hz, 1H), 7.79e7.75 (m, 3H), 7.48 (td, J ¼ 8.0, 0.8 Hz, 1H), 7.37
(br, 1H), 7.29 (d, J ¼ 8.0 Hz, 2H), 7.00 (d, J ¼ 9.2 Hz, 2H), 3.87 (s, 3H),
4H), 2.44 (s, 6H). 13C NMR (125 MHz, CDCl3)
d 160.6, 156.9, 153.3 (d,
JC-F ¼ 241.25 Hz), 151.1, 138.4, 137.8, 132.9, 132.1, 129.3, 127.4, 126.4,
2.42 (s, 3H). 13C NMR (125 MHz, CDCl3)
d 160.5, 157.5, 156.4, 151.0,
126.2, 124.3 (d, JC-F ¼ 3.5 Hz), 123.6 (d, JC-F ¼ 7.625 Hz), 122.7, 120.1,
140.3, 136.0, 132.7, 131.7, 129.1, 128.5, 125.7, 123.3, 120.2, 114.2, 113.7,
55.6, 21.5.
114.8 (d, JC-F ¼ 19.25 Hz), 114.0, 21.5. IR (neat)
n 2993, 2900, 1628,
1568, 1535, 1503, 1482, 1449, 1417, 1353, 1260, 1177, 1113, 1066, 894,
859, 787, 751, 669 cmꢁ1. HRMS (ESI) Calcd for C22H19FN3 [M þ Hþ]
344.1558, found 344.1571.
4.2.1.16. Compound 4p: white solid. m.p. 177.0e179.0 ꢀC. 1H NMR
(500 MHz, CDCl3, TMS)
d
8.38 (d, J ¼ 8.0 Hz, 2H), 7.93 (d, J ¼ 8.0 Hz,
1H), 7.79e7.71 (m, 4H), 7.44e7.41 (m, 2H), 7.27 (d, J ¼ 8.0 Hz, 2H),
4.2.1.22. Compound 4v [10]: white solid. 1H NMR (500 MHz, CDCl3,
7.10 (t, J ¼ 8.5 Hz, 2H), 2.40 (s, 3H). 13C NMR (125 MHz, CDCl3)
TMS)
J ¼ 8.4 Hz, 1H), 7.69 (t, J ¼ 7.6 Hz, 1H), 7.50e7.40 (m, 7H), 7.36e7.28
(m, 2H), 5.07 (s, 2H), 3.38 (s, 3H). 13C NMR (125 MHz, CDCl3)
163.9,
d
8.56 (dd, J ¼ 7.2, 1.6 Hz, 2H), 7.97 (d, J ¼ 8.4 Hz, 1H), 7.94 (d,
d
160.3, 159.3 (d, JC-F ¼ 242.0 Hz), 157.3, 151.0, 140.4, 135.8, 134.6,
132.8, 129.1, 128.4, 125.8, 123.2 (d, JC-F ¼ 7.75 Hz), 120.1, 115.5 (d, JC-
d
¼ 22.375 Hz), 113.6, 21.4. IR (neat)
n
2978, 2903, 1679, 1607, 1575,
159.3, 153.1, 132.1, 130.0, 128.83, 128.81, 128.4, 127.4, 127.3, 124.9,
124.4, 114.8, 56.9, 39.4.
F
1503, 1442, 1399, 1360, 1317, 1213, 1063, 837, 755 cmꢁ1. HRMS (ESI)
Calcd for C21H17FN3 [M þ Hþ] 330.1401, found 330.1396.
4.2.1.23. Compound 4w: yellow solid. m.p. 87.5e88.7 ꢀC. 1H NMR
4.2.1.17. Compound 4q: white solid. m.p. 165.7e166.5 ꢀC. 1H NMR
(500 MHz, CDCl3, TMS)
(400 MHz, CDCl3, TMS)
d
8.34 (d, J ¼ 7.6 Hz, 1H), 8.24 (dd, J ¼ 9.2,
d
7.97 (d, J ¼ 8.0 Hz, 1H), 7.88 (d, J ¼ 8.5 Hz,
1.2 Hz, 1H), 7.92 (d, J ¼ 8.4 Hz, 2H), 7.71e7.67 (m, 1H), 7.46e7.41 (m,
1H), 7.38e7.35 (m, 1H), 7.14 (td, J ¼ 8.4, 2.8 Hz, 1H), 3.82 (q,
J ¼ 7.2 Hz, 4H), 1.45 (t, J ¼ 7.2 Hz, 6H). 13C NMR (125 MHz, CDCl3)
1H), 7.85 (d, J ¼ 7.0 Hz, 1H), 7.79 (t, J ¼ 8.0 Hz, 1H), 7.71 (dd, J ¼ 7.0,
5.0 Hz, 2H), 7.55e7.50 (m, 2H), 7.32e7.25 (m, 3H), 7.05 (t, J ¼ 8.5 Hz,
2H), 2.55 (s, 3H). 13C NMR (125 MHz, CDCl3)
d
163.4, 159.4 (d, JC-
d
163.1 (d, JC-F ¼ 242.375 Hz), 162.6, 158.0 (d, JC-F ¼ 3.125 Hz), 153.0,
¼ 242.25 Hz), 157.2, 150.7, 139.3, 137.2, 134.5, 132.9, 131.1, 130.4,
141.7 (d, JC-F ¼ 7.625 Hz), 131.9, 129.6 (d, JC-F ¼ 7.875 Hz), 129.0,
124.7, 124.4, 123.9 (d, JC-F ¼ 2.625 Hz), 116.6 (d, JC-F ¼ 21.375 Hz),
F
129.2,128.9,126.2,125.7,123.5 (d, JC-F ¼ 7.875 Hz),120.2,115.5 (d, JC-
¼ 22.375 Hz), 113.0, 21.2. IR (neat) 2982, 2896, 1625, 1568, 1510,
n
115.2 (d, JC-F ¼ 4.125 Hz), 115.0. 45.1, 13.1. IR (neat)
n 2971, 2896,
F
1424, 1403, 1353, 1224, 1152, 1052, 952, 837, 805, 758, 733 cmꢁ1
.
1600,1560,1514,1471,1410,1378,1346,1288,1213,1145,1063,1013,
859, 755, 726 cmꢁ1. HRMS (ESI) Calcd for C18H19FN3 [M þ Hþ]
296.1558, found 296.1568.
HRMS (ESI) Calcd for C21H17FN3 [M þ Hþ] 330.1401, found 330.1409.
4.2.1.18. Compound 4r: yellow solid. m.p. 165.3e167.2 ꢀC. 1H NMR
(400 MHz, CDCl3, TMS)
d
8.12e8.10 (m, 2H), 8.00 (d, J ¼ 8.4 Hz, 1H),
4.2.1.24. Compound 4x [11]: white solid. 1H NMR (400 MHz, CDCl3,
7.88e7.79 (m, 4H), 7.53 (t, J ¼ 7.2 Hz, 1H), 7.42 (br, 1H), 7.39 (d,
J ¼ 7.6 Hz, 1H), 7.16 (t, J ¼ 8.8 Hz, 2H), 7.03 (dd, J ¼ 7.6, 1.6 Hz, 1H),
TMS)
d
8.44 (d, J ¼ 8.4 Hz, 2H), 7.90 (t, J ¼ 8.4 Hz, 2H), 7.68e7.64 (m,
1H), 7.35e7.31 (m, 1H), 7.28 (d, J ¼ 8.0 Hz, 2H), 3.80 (q, J ¼ 7.2 Hz,
3.92 (s, 3H). 13C NMR (125 MHz, CDCl3)
d 160.1, 159.8, 159.4 (d, JC-
4H), 2.42 (s, 3H), 1.44 (t, J ¼ 7.2 Hz, 6H). 13C NMR (125 MHz, CDCl3)
¼ 242.75 Hz), 157.4, 151.1, 140.1, 134.6, 132.9, 129.4 (d, JC-
d 162.6, 159.3, 153.1, 139.8, 136.4, 131.7, 128.9, 128.8, 128.3, 124.6,
F
¼ 8.625 Hz), 126.1, 123.5 (d, JC-F ¼ 7.75 Hz), 121.0, 120.1, 117.0, 115.6
123.9, 115.1, 45.0, 21.4, 13.1.
F
(d, JC-F ¼ 22.375 Hz), 113.7, 113.0, 55.3. IR (neat)
n 2978, 2903, 1564,
1521, 1424, 1353, 1224, 1063, 1041, 902, 869, 816, 758, 737 cmꢁ1
.
4.2.1.25. Compound 4y: white solid. m.p. 91.1e91.6 ꢀC. 1H NMR
HRMS (ESI) Calcd for C21H17FN3O [M þ Hþ] 346.1350, found
(500 MHz, CDCl3, TMS)
d
7.94 (d, J ¼ 8.5 Hz, 1H), 7.91 (d, J ¼ 8.5 Hz,
346.1365.
1H), 7.87e7.85 (m, 1H), 7.69 (t, J ¼ 7.5 Hz,1H), 7.39 (t, J ¼ 7.5 Hz, 1H),
7.30e7.28 (m, 3H), 3.79 (q, J ¼ 7.0 Hz, 4H), 2.59 (s, 3H), 1.41 (t,
4.2.1.19. Compound 4s: yellow solid. m.p. 173.6e175.3 ꢀC. 1H NMR
(400 MHz, CDCl3, TMS)
J ¼ 7.0 Hz, 6H). 13C NMR (125 MHz, CDCl3)
d 162.6, 162.5, 152.7,
d
8.45 (d, J ¼ 8.8 Hz, 2H), 7.94 (d, J ¼ 8.4 Hz,
139.8, 137.1, 131.8, 130.9, 130.3, 128.9, 128.5, 125.6, 124.7, 124.3,
1H), 7.83e7.74 (m, 4H), 7.45 (t, J ¼ 8.0 Hz, 1H), 7.41 (br, 1H), 7.14 (t,
114.6, 45.0, 21.2, 13.4. IR (neat) n 2989, 2907, 1603, 1553, 1517, 1381,
J ¼ 8.8 Hz, 2H), 7.00 (d, J ¼ 8.8 Hz, 2H), 3.87 (s, 3H). 13C NMR
1242, 1177, 1070, 869, 823, 794, 762, 733 cmꢁ1. HRMS (ESI) Calcd for
(125 MHz, CDCl3)
d
161.6, 160.1, 159.4 (d, JC-F ¼ 242.0 Hz), 157.3,
C
19H22N3 [M þ Hþ] 292.1808, found 292.1817.
151.2, 134.6, 132.9, 131.2, 130.0, 129.1, 125.6, 123.3 (d, JC-F ¼ 7.75 Hz),
120.1, 115.6 (d, JC-F ¼ 22.375 Hz), 113.7, 113.4, 55.3. IR (neat)
n
2989,
4.2.1.26. Compound 4z: white solid. m.p. 87.1e89.0 ꢀC. 1H NMR
(500 MHz, CDCl3, TMS)
8.54 (dd, J ¼ 8.5, 5.5 Hz, 2H), 7.90 (d,
2900, 1611, 1568, 1532, 1507, 1449, 1414, 1356, 1220, 1170, 1056,
1027, 948, 862, 826, 758 cmꢁ1. HRMS (ESI) Calcd for C21H17FN3O
[M þ Hþ] 346.1350, found 346.1355.
d
J ¼ 8.5 Hz, 2H), 7.68 (t, J ¼ 7.0 Hz, 1H), 7.35 (t, J ¼ 7.0 Hz, 1H), 7.15 (t,
J ¼ 8.5 Hz, 2H), 3.82 (q, J ¼ 6.5 Hz, 4H), 1.45 (t, J ¼ 6.5 Hz, 6H). 13
C
NMR (125 MHz, CDCl3)
d
164.3 (d, JC-F ¼ 247.5 Hz), 162.6, 158.3,
4.2.1.20. Compound 4t: yellow solid. m.p. 159.2e160.1 ꢀC. 1H NMR
(400 MHz, CDCl3, TMS)
1H), 7.58e7.53 (m, 1H), 7.38 (t, J ¼ 8.0 Hz, 2H), 7.32 (d, J ¼ 8.0 Hz,
153.0, 135.2, 131.9, 130.3 (d, JC-F ¼ 8.5 Hz), 128.8, 124.7, 124.1, 115.02
(d, JC-F ¼ 21.375 Hz), 115.00, 45.1, 13.1. IR (neat) 2980, 2919, 1596,
1558, 1505, 1463, 1376, 1353, 1206, 1065, 845, 796, 751, 682 cmꢁ1
d
8.52 (d, J ¼ 8.0 Hz, 2H), 7.90 (d, J ¼ 8.4 Hz,
n
.
Please cite this article as: Z. Bao et al., N-heterocyclic carbene-Pd(II)-1-methylimidazole complex-catalyzed Suzuki-Miyaura coupling of 2-