M. Kim et al. / Tetrahedron 69 (2013) 6552e6559
6557
777 cmꢂ1; HRMS (EI) m/z calcd for C20H14FNO4 [M]þ 351.0907;
1064, 888, 777 cmꢂ1; HRMS (EI) m/z calcd for C22H14FNO2 [M]þ
found 351.0916.
343.1009; found 343.1013.
4.3.11. (3-Fluoro-2-(pyridin-2-yloxy)phenyl)(naphthalen-2-yl)meth-
4.3.6. (3-Fluoro-2-(pyridin-2-yloxy)phenyl)(4-(trifluoromethyl)phe-
nyl)methanone (3f). Rf¼0.56 (n-hexanes/EtOAc¼4:1); colorless oil;
anone (3k). Rf¼0.45 (n-hexanes/EtOAc¼4:1); pale yellow oil; 1H
1H NMR (400 MHz, CDCl3)
d
7.98 (d, J¼4.8 Hz, 1H), 7.79
NMR (400 MHz, CDCl3)
d
8.20 (s, 1H), 8.00 (d, J¼5.0 Hz, 1H), 7.90
(d, J¼8.5 Hz, 1H), 7.80e7.75 (m, 3H), 7.53 (t, J¼6.9 Hz, 1H), 7.47e7.30
(d, J¼8.0 Hz, 2H), 7.53e7.47 (m, 3H), 7.40e7.28 (m, 3H), 6.90
(m, 5H), 6.80e6.77 (m, 1H), 6.59 (d, J¼8.3 Hz, 1H); 13C NMR
(t, J¼5.6 Hz, 1H), 6.59 (d, J¼8.2 Hz, 1H); 13C NMR (100 MHz, CDCl3)
(100 MHz, CDCl3)
d
194.0, 162.1, 155.1 (d, JCeF¼249.5 Hz), 146.7, 139.2,
d
193.2, 161.8, 155.1 (d, JCeF¼250.0 Hz), 146.6, 140.2, 139.4, 139.2
139.1 (d, JCeF¼13.3 Hz), 135.4, 135.1, 134.2, 132.6, 132.0, 129.4, 128.5,
(d, JCeF¼13.5 Hz), 134.1, 134.0 (q, JCeF¼32.6 Hz), 129.7, 125.9
(d, JCeF¼7.4 Hz), 125.1 (d, JCeF¼3.5 Hz), 124.9 (d, JCeF¼3.6 Hz), 123.5
128.0, 127.6, 126.5, 125.8 (d, JCeF¼7.3 Hz), 125.0 (d, JCeF¼3.5 Hz),
124.6,118.9 (d, JCeF¼18.9 Hz),118.6,110.5; IR (KBr)
y 2842,1739,1665,
(q, JCeF¼271.0 Hz), 119.6 (d, JCeF¼19.0 Hz), 118.8, 110.5; IR (KBr)
y
1626, 1596, 1462, 1429, 1270, 1238, 1143, 1068, 882, 772 cmꢂ1; HRMS
2947, 2846, 1677, 1596, 1463, 1403, 1327, 1271, 1171, 1130, 1015, 888,
765 cmꢂ1; HRMS (EI) m/z calcd for C19H11F4NO2 [M]þ 361.0726;
found 361.0730.
(EI) m/z calcd for C22H14FNO2 [M]þ 343.1009; found 343.1014.
4.3.12. 1-(3-Fluoro-2-(pyridin-2-yloxy)phenyl)-3-phenylpropan-1-
one (3l). Rf¼0.55 (n-hexanes/EtOAc¼4:1); pale yellow oil; 1H NMR
4.3.7. (3-Fluoro-2-(pyridin-2-yloxy)phenyl)(4-fluorophenyl)meth-
anone (3g). Rf¼0.60 (n-hexanes/EtOAc¼4:1); colorless oil; 1H NMR
(700 MHz, CDCl3)
d
8.10 (d, J¼5.0 Hz, 1H), 7.75 (t, J¼7.2 Hz, 1H), 7.55
(d, J¼7.8 Hz, 1H), 7.31e7.24 (m, 2H), 7.22e7.20 (m, 2H), 7.11
(d, J¼7.3 Hz, 1H), 7.08 (d, J¼8.2 Hz, 2H), 7.02e7.00 (m, 2H), 3.18
(t, J¼7.4 Hz, 2H), 2.94 (t, J¼7.7 Hz, 2H); 13C NMR (175 MHz, CDCl3)
(400 MHz, CDCl3)
d
7.99 (d, J¼5.0 Hz, 1H), 7.97e7.75 (m, 2H), 7.53
(t, J¼8.4 Hz, 1H), 7.36e7.27 (m, 3H), 6.97 (t, J¼8.6 Hz, 2H), 6.89
(t, J¼5.0 Hz, 1H), 6.67 (d, J¼8.3 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d
199.2, 162.3, 155.2 (d, JCeF¼249.2 Hz), 147.4, 140.8, 139.9
d
192.5, 165.7 (d, JCeF¼253.6 Hz), 162.1, 155.1 (d, JCeF¼249.9 Hz),
(d, JCeF¼13.2 Hz), 139.7, 135.4, 134.4, 132.6, 128.3, 128.1, 125.9, 125.8
(d, JCeF¼7.2 Hz),124.7 (d, JCeF¼3.5 Hz),119.9 (d, JCeF¼18.5 Hz),119.0,
146.7, 139.4, 138.9 (d, JCeF¼13.2 Hz), 134.6, 134.8, 133.5
(d, JCeF¼2.8 Hz), 132.5 (d, JCeF¼9.3 Hz), 125.8 (d, JCeF¼7.3 Hz), 124.7
(d, JCeF¼3.6 Hz), 119.1 (d, JCeF¼18.9 Hz), 118.7, 115.2
110.7, 44.0, 29.8; IR (KBr) y 2966, 2877, 1691, 1597, 1462, 1430, 1270,
1236, 1143, 884, 777 cmꢂ1; HRMS (EI) m/z calcd for C20H16FNO2
(d, JCeF¼21.8 Hz), 110.6; IR (KBr)
y 2946, 1671, 1597, 1462, 1429, 1271,
[M]þ 321.1165; found 321.1161.
1237, 1153, 1068, 888, 776 cmꢂ1; HRMS (EI) m/z calcd for
C18H11F2NO2 [M]þ 311.0758; found 311.0758.
4.3.13. 1-(3-Fluoro-2-(pyridin-2-yloxy)phenyl)butan-1-one
(3m). Rf¼0.55 (n-hexanes/EtOAc¼4:1); colorless oil; 1H NMR
4.3.8. (3-Chlorophenyl)(3-fluoro-2-(pyridin-2-yloxy)phenyl)meth-
anone (3h). Rf¼0.50 (n-hexanes/EtOAc¼4:1); colorless oil; 1H NMR
(400 MHz, CDCl3)
d
8.09 (d, J¼5.0 Hz, 1H), 7.72 (t, J¼7.2 Hz, 1H), 7.54
(d, J¼7.2 Hz, 1H), 7.31e7.21 (m, 2H), 7.04e6.98 (m, 2H), 2.79
(400 MHz, CDCl3)
d
8.00 (d, J¼4.9 Hz, 1H), 7.69 (s, 1H), 7.61
(t, J¼7.2 Hz, 2H), 1.62e1.58 (m, 2H), 0.81 (t, J¼7.4 Hz, 3H); 13C NMR
(d, J¼7.7 Hz, 1H), 7.53 (t, J¼7.2 Hz, 1H), 7.41e7.21 (m, 5H), 6.89
(100 MHz, CDCl3)
d
200.4, 162.3, 155.2 (d, JCeF¼248.7 Hz), 147.4,
(t, J¼5.4 Hz, 1H), 6.66 (d, J¼8.3 Hz, 1H); 13C NMR (100 MHz, CDCl3)
139.7, 139.6 (d, JCeF¼13.2 Hz), 134.7, 125.8 (d, JCeF¼7.3 Hz), 124.7
d
192.8, 161.9, 155.1 (d, JCeF¼250.0 Hz), 146.87, 139.4, 139.1
(d, JCeF¼3.4 Hz), 119.7 (d, JCeF¼19.0 Hz), 118.9, 110.6, 44.6, 17.3, 13.6;
(d, JCeF¼13.3 Hz), 138.7, 134.3, 134.2, 132.8, 129.6, 129.3, 127.7, 125.8
(d, JCeF¼7.4 Hz),124.9 (d, JCeF¼3.5 Hz),119.4 (d, JCeF¼18.9 Hz),118.7,
IR (KBr) y 2986, 2848, 1691, 1595, 1460, 1430, 1271, 1238, 1143, 990,
888, 775 cmꢂ1; HRMS (EI) m/z calcd for C15H14FNO2 [M]þ 259.1009;
110.5; IR (KBr) y 2841, 1674, 1596, 1463, 1429, 1270, 1237, 1143, 1073,
found 259.1003.
890, 752 cmꢂ1; HRMS (EI) m/z calcd for C18H11ClFNO2 [M]þ
327.0462; found 327.0463.
4.3.14. (5-Chloro-4-methyl-2-(pyridin-2-yloxy)phenyl)(phenyl)
methanone (4b). Rf¼0.40 (n-hexanes/EtOAc¼4:1); white solid; mp
84e88 ꢀC; 1H NMR (400 MHz, CDCl3)
d
7.98 (d, J¼5.0 Hz, 1H), 7.69
4.3.9. (3-Fluoro-2-(pyridin-2-yloxy)phenyl)(2-fluorophenyl)meth-
anone (3i). Rf¼0.58 (n-hexanes/EtOAc¼4:1); white solid; mp
(d, J¼8.1 Hz, 2H), 7.52 (s, 1H), 7.50e7.43 (m, 2H), 7.30 (t, J¼8.0 Hz,
2H), 7.13 (s, 1H), 6.85 (t, J¼5.0 Hz, 1H), 6.54 (d, J¼8.3 Hz, 1H), 2.41
43e46 ꢀC; 1H NMR (400 MHz, CDCl3)
d
7.98 (d, J¼5.0 Hz, 1H),
(s, 3H); 13C NMR (100 MHz, CDCl3)
d 193.7, 162.7, 149.8, 146.8, 140.7,
7.49e7.45 (m, 2H), 7.43e7.26 (m, 4H), 7.03e6.94 (m, 2H), 6.87
(t, J¼5.0 Hz, 1H), 6.52 (d, J¼8.3 Hz, 1H); 13C NMR (100 MHz, CDCl3)
139.7, 137.2, 132.8, 131.0, 130.5, 130.3, 129.6, 128.0, 125.1, 118.5, 113.3,
20.4; IR (KBr) 2976, 2864, 1740, 1667, 1591, 1462, 1428, 1375, 1262,
d
190.6, 162.1, 160.7 (d, JCeF¼254.3 Hz), 155.1 (d, JCeF¼248.8 Hz),
y
1241, 1131, 1011, 897, 779 cmꢂ1
; HRMS (EI) m/z calcd for
146.8, 139.5 (d, JCeF¼13.6 Hz), 139.2, 135.1, 133.7 (d, JCeF¼8.4 Hz),
130.7 (d, JCeF¼1.6 Hz),127.3 (d, JCeF¼12.2 Hz),125.8 (d, JCeF¼7.3 Hz),
125.2 (d, JCeF¼3.4 Hz), 123.8 (d, JCeF¼3.6 Hz), 120.1
C19H14ClNO2 [M]þ 323.0713; found 323.0714.
(d, JCeF¼19.1 Hz), 118.5, 116.0 (d, JCeF¼21.7 Hz), 110.2; IR (KBr)
y
4.3.15. (4,5-Dimethoxy-2-(pyridin-2-yloxy)phenyl)(phenyl)meth-
2841, 1673, 1609, 1463, 1429, 1307, 1271, 1236, 1103, 1070, 888,
774 cmꢂ1; HRMS (EI) m/z calcd for C18H11F2NO2 [M]þ 311.0758;
found 311.0754.
anone (4c). Rf¼0.35 (n-hexanes/EtOAc¼4:1); pale yellow sticky
solid; 1H NMR (400 MHz, CDCl3)
d
8.07 (d, J¼5.1 Hz, 1H), 7.62
(d, J¼8.4 Hz, 2H), 7.56 (t, J¼8.5 Hz, 1H), 7.43 (t, J¼7.4 Hz, 1H), 7.29
(t, J¼7.8 Hz, 2H), 7.12 (s, 1H), 6.93 (t, J¼5.5 Hz, 1H), 6.76 (s, 1H), 6.49
(d, J¼8.3 Hz, 1H), 3.90 (s, 3H), 3.88 (s, 3H); 13C NMR (100 MHz,
4.3.10. (3-Fluoro-2-(pyridin-2-yloxy)phenyl)(naphthalen-1-yl)meth-
anone (3j). Rf¼0.45 (n-hexanes/EtOAc¼4:1); yellow sticky solid; 1H
CDCl3):
d
¼190.8, 162.5, 152.5, 146.3, 145.7, 145.3, 140.6, 138.0, 132.4,
NMR (400 MHz, CDCl3)
d
8.30 (d, J¼9.7 Hz, 1H), 7.90 (d, J¼5.0 Hz,
129.4, 127.9, 123.2, 118.2, 112.5, 113.3, 106.2, 56.3, 56.2; IR (KBr)
y
1H), 7.77e7.71 (m, 2H), 7.50 (d, J¼7.1 Hz, 1H), 7.46e7.43 (m, 3H),
2976, 2864, 1659, 1599, 1512, 1449, 1428, 1271, 1241, 1216, 1106,
1006, 868, 780 cmꢂ1; HRMS (EI) m/z calcd for C20H17NO4 [M]þ
335.1158; found 335.1157.
7.38e7.16 (m, 4H), 6.72e6.70 (m, 1H), 6.24 (d, J¼8.3 Hz, 1H); 13C
NMR (100 MHz, CDCl3)
d
195.5, 161.9, 155.4 (d, JCeF¼249.3 Hz),
146.6, 139.7 (d, JCeF¼13.2 Hz), 138.9, 136.0, 135.5, 133.4, 132.3, 130.3,
129.8, 128.1, 127.6, 126.2, 125.8 (d, JCeF¼3.5 Hz), 125.7 (d,
JCeF¼7.3 Hz), 125.5, 123.9, 119.8 (d, JCeF¼19.1 Hz), 118.4, 110.3; IR
4.3.16. Phenyl(3-(pyridin-2-yloxy)naphthalen-2-yl)methanone
(4d). Rf¼0.40 (n-hexanes/EtOAc¼4:1); pale yellow sticky solid; 1H
(KBr)
y 2946, 2844, 1739, 1665, 1594, 1462, 1429, 1270, 1235, 1143,
NMR (400 MHz, CDCl3)
d
8.07 (s, 1H), 7.94 (d, J¼4.8 Hz, 1H),