W. Ren et al. / Tetrahedron 68 (2012) 1351e1358
1357
HRMS (ESI): m/z calcd for [C11H8FNþH]þ: 174.0719, found:
1H), 7.89 (q, J¼15.8, 7.7 Hz,1H), 8.56 (dd, J¼4.8, 3.1 Hz,1H); 13C NMR
174.0716.
(100 MHz, CDCl3, ppm):
d
23.5, 108.1 (d, J¼36.8 Hz), 121.1, 121.3 (d,
J¼4.2 Hz), 134.0, 137.3, 141.4 (d, J¼7.8 Hz), 149.1, 156.1, 156.7 (d,
J¼13.6 Hz), 163.0 (d, J¼238.6 Hz); HRMS (ESI): m/z calcd for
[C11H9FN2þH]þ: 189.0828, found: 189.0816.
4.6.12. 2-Fluoro-6-(1-naphthalenyl)pyridine (Table 3, entry 12)
(3al). Yellow oil; 68% yield. 1H NMR (400 MHz, CDCl3, ppm):
d 6.98
(dd, J¼5.1, 7.9 Hz, 1H), 7.47e7.57 (m, 4H), 7.63 (dd, J¼5.9, 7.1 Hz, 1H),
7.87e7.94 (m, 3H), 8.15 (q, J¼5.5, 11.0 Hz, 1H,); 13C NMR (100 MHz,
4.6.19. 6-Fluoro-2,40-bipyridine (Table 4, entry 7) (3bg). White
solid; mp 81e83 ꢀC; 78% yield. 1H NMR (400 MHz, CDCl3, ppm):
CDCl3, ppm):
d
107.7 (d, J¼36.8 Hz), 122.2 (d, J¼4.1 Hz), 125.2 (d,
J¼4.4 Hz), 126.0, 126.7, 127.7, 128.4, 129.4, 130.8, 133.8, 136.6, 141.3
(d, J¼7.7 Hz),157.8 (d, J¼13.5 Hz), 163.1 (d, J¼237.9 Hz); HRMS (ESI):
m/z calcd for [C15H10FNþH]þ: 224.0876, found: 224.0874.
d
6.99 (dd, J¼5.6, 8.4 Hz, 1H), 7.71 (dd, J¼5.6, 7.9 Hz, 1H), 7.87e7.95
(m, 3H), 8.74 (d, J¼4.6 Hz, 2H); 13C NMR (100 MHz, CDCl3, ppm):
d
108.9 (d, J¼37.2 Hz), 116.9 (d, J¼3.9 Hz), 119.9, 141.1 (d, J¼7.7 Hz),
143.5, 149.6,152.4 (d, J¼13.2 Hz), 162.5 (d, J¼238.9 Hz); HRMS (ESI):
4.6.13. 6-Fluoro-60-methoxy-2,20-bipyridine (Table 4, entries 1 and
m/z calcd for [C10H7FN2þH]þ: 175.0672, found: 175.0660.
10) (3ba). White solid; mp 78e79 ꢀC; 82% and 65% yield. 1H NMR
(400 MHz, CDCl3, ppm):
d
4.03 (s, 3H), 6.79 (d, J¼8.2 Hz, 1H), 6.92
4.6.20. 6-Fluoro-N-methyl-2,30-bipyridin-50-amine (Table 4, entry 8)
(dd, J¼5.2, 8.1 Hz, 1H), 7.69 (t, J¼7.9 Hz, 1H), 7.89 (q, J¼7.9, 15.9 Hz,
(3bh). White solid; mp 104e106 ꢀC; 61% yield. 1H NMR (400 MHz,
1H), 7.96 (d, J¼7.4 Hz, 1H), 8.30 (dd, J¼5.3, 7.5 Hz, 1H); 13C NMR
CDCl3, ppm):
d
2.98 (d, J¼5.1 Hz, 3H), 4.77 (s, 1H), 6.92 (dd, J¼5.1,
(100 MHz, CDCl3, ppm):
d
53.2, 109.1 (d, J¼37.3 Hz), 111.7, 114.0,
8.1 Hz, 1H), 7.02 (s, 1H), 7.06 (d, J¼5.3 Hz, 1H), 7.61 (dd, J¼5.1, 7.5 Hz,
117.9, 139.4, 141.6 (d, J¼7.6 Hz), 151.7, 154.8 (d, J¼13.0 Hz), 162.9 (d,
J¼236.6 Hz), 163.4; HRMS (ESI): m/z calcd for [C11H9FN2OþH]þ:
205.0777, found: 205.0773.
1H), 7.85 (q, J¼7.9, 15.8 Hz, 1H), 8.17 (d, J¼5.3 Hz, 1H); 13C NMR
(100 MHz, CDCl3, ppm):
d
29.2, 103.7, 109.4 (d, J¼37.6 Hz), 110.2,
117.9 (d, J¼3.9 Hz), 141.8 (d, J¼7.7 Hz), 146.0, 148.8, 154.3 (d,
J¼13.1 Hz), 160.3, 163.3 (d, J¼237.9 Hz); HRMS (ESI): m/z calcd for
[C11H10FN3þH]þ: 204.0937, found: 204.0938.
4.6.14. 6-Fluoro-2,20-bipyridine (Table 4, entry 2) (3bb). Yellow
solid; mp 70e72 ꢀC; 27% yield. 1H NMR (400 MHz, CDCl3, ppm):
d
6.95 (dd, J¼5.3, 8.0 Hz, 1H), 7.33 (dd, J¼1.8, 6.9 Hz, 1H), 7.81 (q, 7.0,
4.6.21. 2-(6-Fluoro-2-pyridinyl)quinoline (Table 4, entry 9) (3bi). -
White solid; mp 110e112 ꢀC; 64% yield. 1H NMR (400 MHz, CDCl3,
14.5 Hz, 1H), 7.90e7.92 (m, 1H), 8.31 (dd, J¼5.6, 7.6 Hz, 1H), 8.35 (d,
J¼8.0 Hz, 1H), 8.67 (d, J¼4.3 Hz, 1H); 13C NMR (100 MHz, CDCl3,
ppm):
d
7.01 (dd, J¼5.5, 8.3 Hz, 1H), 7.55e7.59 (m, 1H), 7.73e7.77
ppm):
d
109.4 (d, J¼37.1 Hz), 118.1 (d, J¼3.9 Hz), 121.3, 124.2, 137.0,
(m, 1H), 7.86 (d, J¼7.3 Hz, 1H), 7.97 (q, J¼7.8, 15.9 Hz, 1H), 8.17 (d,
J¼8.5 Hz, 1H), 8.29 (d, J¼8.6 Hz, 1H), 8.51 (d, J¼8.6 Hz, 1H), 8.58 (dd,
141.8 (d, J¼7.5 Hz), 149.2, 154.5, 154.9 (d, J¼12.9 Hz), 163.1 (d,
J¼237.1 Hz); HRMS (ESI): m/z calcd for [C10H7FN2þH]þ: 175.0672,
found: 175.0663.
J¼5.0, 7.3 Hz, 1H); 13C NMR (100 MHz, CDCl3, ppm):
d 109.8 (d,
J¼37.1 Hz), 118.9 (d, J¼3.1 Hz), 127.1, 127.7, 128.4, 129.8 (d, J¼8.7 Hz),
137.0, 141.9 (d, J¼7.4 Hz), 147.9, 154.6, 155.1 (d, J¼12.6 Hz), 163.2 (d,
J¼237.3 Hz); HRMS (ESI): m/z calcd for [C14H9FN2þH]þ: 225.0828,
found: 225.0825.
4.6.15. 6-Fluoro-2,30-bipyridine (Table 4, entry 3) (3bc). Yellow solid;
mp 36e38 ꢀC; 78% yield. 1H NMR (400 MHz, CDCl3, ppm):
d 6.94
(dd, J¼5.2, 8.2 Hz, 1H), 7.42 (q, J¼3.3, 7.9 Hz, 1H), 7.67 (dd, J¼5.1,
7.6 Hz, 1H), 7.90 (q, J¼7.7, 15.8 Hz, 1H), 8.3 (d, J¼4.0 Hz, 1H), 8.67 (d,
4.6.22. 2-(6-Fluoropyridin-2-yl)-6-phenylpyrazine (Table 4, entry 11)
J¼3.9 Hz, 1H), 9.20 (s, 1H); 13C NMR (100 MHz, CDCl3, ppm):
d
108.6
(3bk). White solid; mp 58e60 ꢀC; 59% yield. 1H NMR (400 MHz,
(d, J¼37.1 Hz), 117.4 (d, J¼3.9 Hz), 123.6, 133.1, 134.3, 141.9 (d,
J¼7.7 Hz), 148.1, 150.4, 153.5 (d, J¼13.4 Hz), 163.5 (d, J¼238.4 Hz);
HRMS (ESI): m/z calcd for [C10H7FN2þH]þ: 175.0672, found:
175.0665.
CDCl3, ppm):
d
7.04 (dd, J¼5.4, 8.3 Hz, 1H), 7.52e7.58 (m, 3H), 7.98
(q, J¼7.7, 15.4 Hz, 1H), 8.15 (d, J¼8.3 Hz, 2H), 8.48 (dd, J¼5.6, 8.1 Hz,
1H), 9.08 (s, 1H), 9.51 (s, 1H); 13C NMR (100 MHz, CDCl3, ppm):
d
110.4 (d, J¼36.9 Hz), 118.7 (d, J¼3.9 Hz), 127.0, 129.0, 130.1, 136.1,
141.1, 142.0 (d, J¼6.4 Hz), 148.5, 151.1, 153.2 (d, J¼13.4 Hz), 163.1 (d,
J¼238.3 Hz); HRMS (ESI): m/z calcd for [C15H10FN3þH]þ: 252.0937,
found: 252.0930.
4.6.16. 6-Fluoro-2,30-bipyridin-60-amine (Table 4, entry 4) (3bd).
White solid; mp 139e141 ꢀC; 89% yield. 1H NMR (400 MHz, CDCl3,
ppm):
d
4.66 (s, 2H), 6.59 (d, J¼8.2 Hz, 1H), 6.80 (dd, J¼4.9, 7.9 Hz,
1H), 7.51 (dd, J¼5.2, 7.8 Hz, 1H), 7.80 (q, J¼7.7, 15.8 Hz, 1H), 8.12 (dd,
4.6.23. 2-Benzo[b]thiophen-5-yl-6-fluoropyridine (Table 4, entry 12)
(3bl). White solid; mp 111e113 ꢀC; 94% yield. 1H NMR (400 MHz,
J¼6.1, 8.5 Hz, 1H), 8.70 (s, 1H); 13C NMR (100 MHz, CDCl3, ppm):
d
106.8 (d, J¼37.4 Hz), 108.4, 115.8 (d, J¼4.0 Hz), 124.0, 136.5, 141.6
CDCl3, ppm):
d
6.87 (dd, J¼4.9, 8.0 Hz, 1H), 7.42 (d, J¼5.4 Hz, 1H),
(d, J¼7.8 Hz), 147.1, 154.4 (d, J¼13.7 Hz), 159.1, 163.5 (d, J¼236.8 Hz);
HRMS (ESI): m/z calcd for [C10H8FN3þH]þ: 190.0781, found:
190.0775.
7.49 (d, J¼5.4 Hz, 1H), 7.70 (dd, J¼5.0, 7.7 Hz, 1H), 7.86 (q, J¼7.7,
15.9 Hz, 1H), 7.94e7.98 (m, 2H), 8.49 (s, 1H); 13C NMR (100 MHz,
CDCl3, ppm):
d
107.5 (d, J¼37.4 Hz), 117.3 (d, J¼3.6 Hz), 122.2, 122.8,
122.9, 124.4, 127.3, 134.0, 140.1, 141.0, 141.7 (d, J¼7.6 Hz), 156.4 (d,
J¼13.5 Hz), 163.4 (d, J¼236.6 Hz); HRMS (ESI): m/z calcd for
[C13H8FNSþH]þ: 230.0440, found: 230.0441.
4.6.17. 6-Fluoro-60-(trifluoromethyl)-2,30-bipyridine (Table 4, entry
5) (3be). Yellow solid; mp 102e104 ꢀC; 94% yield. 1H NMR
(400 MHz, CDCl3, ppm):
d
6.92 (dd, J¼8.1, 5.2 Hz, 1H), 7.63 (dd,
J¼7.5, 5.1 Hz, 1H), 7.70 (d, J¼8.2 Hz, 1H), 7.86 (q, J¼15.8, 7.8 Hz, 1H),
4.6.24. 6-Methoxy-60-(trifluoromethyl)-2,30-bipyridine (Table 5, en-
try 1) (3ca). Yellow solid; mp 59e61 ꢀC; 80% yield. 1H NMR
8.42 (dd, J¼8.2, 6.5 Hz, 1H), 9.19 (s, 1H); 13C NMR (100 MHz, CDCl3,
ppm):
d
109.6 (d, J¼6.6 Hz), 110.0,118.0,120.5, 125.6 (q, J¼272.6 Hz),
(400 MHz, CDCl3, ppm):
J¼7.3 Hz, 1H), 7.66e7.76 (m, 2H), 8.48 (d, J¼8.2 Hz, 1H), 9.33 (s, 1H);
13C NMR (100 MHz, CDCl3, ppm):
53.3, 111.4, 113.4, 120.2, 125.7 (q,
d
4.04 (s, 3H), 6.79 (d, J¼8.2 Hz,1H), 7.39 (d,
135.8, 142.3 (d, J¼7.8 Hz), 148.2, 149.1 (q, J¼34.7 Hz), 151.9 (d,
J¼13.5 Hz), 163.6 (d, J¼239.7 Hz); HRMS (ESI): m/z calcd for
[C11H6F4N2þH]þ: 243.0545, found: 243.0546.
d
J¼272.2 Hz), 135.1, 137.1, 139.4, 147.5, 148.3, 150.3, 164.1; HRMS
(ESI): m/z calcd for [C12H9F3N2OþH]þ: 255.0745, found: 255.0744.
4.6.18. 6-Fluoro-20-methyl-2,30-bipyridine (Table 4, entry 6)
(3bf). White solid; mp 96e97 ꢀC; 75% yield. 1H NMR (400 MHz,
4.6.25. 4-(6-Methoxypyridin-2-yl)benzonitrile (Table 5, entry 2)
CDCl3, ppm):
d
2.64 (s, 3H), 6.95 (dd, J¼8.2, 5.4 Hz, 1H,), 7.23 (q,
(3cb). White solid; mp 78e80 ꢀC; 83% yield. 1H NMR (400 MHz,
J¼7.8, 2.9 Hz, 1H), 7.33 (dd, J¼7.7, 5.4 Hz, 1H), 7.74 (dd, J¼7.8, 6.0 Hz,
CDCl3, ppm):
d
3.97 (s, 3H), 6.71 (d, J¼8.2 Hz, 1H), 7.32 (d, J¼7.4 Hz,