N.A. Markina et al. / Tetrahedron 69 (2013) 2701e2713
2711
(s, 3H), 4.40 (q, J¼7.1 Hz, 2H), 6.41e6.48 (m, 1H), 7.47 (d, J¼8.5 Hz, 1H),
7.54 (t, J¼7.7 Hz, 1H), 7.61e7.66 (m, 1H), 8.01 (dd, J¼10.8, 1.5 Hz, 2H),
8.09 (d, J¼7.8 Hz, 1H), 8.13 (d, J¼1.9 Hz, 1H); 13C NMR (100 MHz,
129.8, 130.1, 133.6, 133.6, 149.9, 151.4, 154.0; HRMS calcd for
C
20H13NO3 [MþH]þ 316.0968, found 316.0977.
CDCl3)
d
14.5, 21.9, 22.6, 25.9, 26.6, 52.2, 61.3, 110.8, 115.5, 121.9, 125.2,
4.3.21. 3-(4-Chlorophenyl)-2-phenylbenzofuran (46). Yellow solid,
145.6 mg (96%): mp 100e101 ꢁC; 1H NMR (400 MHz, CDCl3)
126.4, 127.9, 128.9, 128.9, 130.6, 131.0, 131.1, 131.2, 133.2, 134.5, 154.5,
156.0, 166.6, 167.4; HRMS calcd for C25H25O5 [MþH]þ 405.1697, found
405.1706.
d
7.24e7.28 (m, 1H), 7.35 (dd, J¼10.2, 5.7 Hz, 4H), 7.45 (s, 4H), 7.47
(d, J¼7.8 Hz, 1H), 7.57 (d, J¼8.2 Hz, 1H), 7.64 (dd, J¼7.9, 1.7 Hz, 2H);
13C NMR (100 MHz, CDCl3)
111.4, 116.5, 119.9, 123.3, 125.1, 127.3,
d
4.3.13. Ethyl 4-[2-(thiophen-3-yl)benzofuran-3-yl]benzoate (31). Yell-
128.7, 128.8, 129.5, 130.0, 130.5, 131.3, 131.5, 133.7, 143.7, 150.9;
ow oil, 174.2 mg (100%): 1H NMR (300 MHz, CDCl3)
d
1.45 (t, J¼7.2 Hz,
HRMS calcd for C20H13ClO [MþH]þ 305.0728, found 305.0731.
3H), 4.44 (q, J¼7.1 Hz, 2H), 7.21 (t, J¼5.2 Hz, 1H), 7.24e7.30 (m, 2H),
7.35 (t, J¼7.6 Hz, 1H), 7.47 (d, J¼7.2 Hz, 1H), 7.55 (d, J¼8.1 Hz, 1H),
7.58e7.70 (m, 3H), 8.18 (d, J¼8.4 Hz, 2H); 13C NMR (75 MHz, CDCl3)
4.3.22. 1-[4-(2-(Thiophen-3-yl)benzofuran-3-yl)phenyl]ethanone
(48). Cream colored solid, 116.1 mg (73%): mp 172e174 ꢁC; 1H NMR
d
14.6, 61.3, 111.3, 115.9, 119.8, 123.4, 123.8, 125.0, 126.1, 126.2, 129.7,
(400 MHz, CDCl3)
d
2.68 (s, 3H), 7.20 (d, J¼5.1 Hz, 1H), 7.27 (dd,
130.0, 130.3, 131.6, 137.7, 148.3, 154.0, 166.6; HRMS calcd for C21H16O3S
J¼7.3, 5.5 Hz, 2H), 7.35 (t, J¼7.7 Hz, 1H), 7.47 (d, J¼7.8 Hz, 1H), 7.55
(d, J¼8.1 Hz, 1H), 7.65 (dd, J¼8.6, 5.6 Hz, 3H), 8.09 (d, J¼8.0 Hz, 2H);
[MþH]þ 349.0893, found 349.0900.
13C NMR (100 MHz, CDCl3)
d 26.9, 111.4, 115.8, 119.8, 123.4, 123.9,
4.3.14. Ethyl 4-[2-(1-methyl-1H-pyrazol-5-yl)benzofuran-3-yl]ben-
125.1, 126.1, 126.3, 129.1, 129.6, 130.2, 131.6, 136.5, 138.1, 148.3, 154.0,
zoate (33). Green amorphous solid, 109.4 mg (63%): 1H NMR
197.9; HRMS calcd for C20H14O2S [MþH]þ 318.0715, found 318.0731.
(400 MHz, CDCl3)
d
1.41 (t, J¼7.1 Hz, 3H), 3.63 (s, 3H), 4.40 (q,
J¼7.1 Hz, 2H), 7.31 (t, J¼7.3 Hz, 1H), 7.38 (t, J¼7.3 Hz, 1H),
7.42e7.49 (m, 1H), 7.55 (t, J¼6.8 Hz, 3H), 7.60e7.72 (m, 2H), 8.11
4.3.23. 3-(2-Phenylbenzofuran-3-yl)-1-tosyl-1H-indole (50). Yellow
amorphous solid, 134.1 mg (58%): 1H NMR (400 MHz, CDCl3)
d 2.40
(d, J¼7.7 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
14.6, 61.3, 111.6,
(s, 3H), 7.14 (t, J¼7.5 Hz, 1H), 7.25 (ddd, J¼21.5, 15.1, 8.0 Hz, 7H), 7.37
(dd, J¼15.9, 8.5 Hz, 3H), 7.57e7.64 (m, 3H), 7.76 (s, 1H), 7.85 (d,
J¼8.2 Hz, 2H), 8.13 (d, J¼8.3 Hz, 1H); 13C NMR (100 MHz, CDCl3)
120.2, 123.7, 125.5, 128.1, 128.6, 128.7, 129.1, 129.9, 130.4,
132.1, 132.2, 132.3, 136.8, 154.8, 166.4 (NeCH3 does not show
up); HRMS calcd for C21H18N2O3 [MþH]þ 347.1390, found
347.1398.
d
21.9, 108.1, 111.5, 114.1, 114.9, 120.3, 121.4, 123.2, 123.7, 125.1, 125.3,
125.4, 126.9, 127.1, 128.6, 128.7, 130.0, 130.2, 130.5, 130.6, 135.4,
135.7, 145.3, 152.1, 154.3; HRMS calcd for C29H21NO3S [MþH]þ
463.1242, found 463.1315.
4.3.15. 2,3-Diphenylbenzofuran (34).22 Yellow-green solid, 117.6 mg
(87%): mp 116e119 ꢁC [lit. mp 123 ꢁC];23 1H NMR (300 MHz, CDCl3)
d
7.20e7.36 (m, 5H), 7.46 (m, 6H), 7.56 (d, J¼8.2 Hz, 1H), 7.66 (d,
4.3.24. 3-(2-Phenylbenzofuran-3-yl)-4H-chromen-4-one (52). Cream
colored solid, 73.4 mg (43%): mp 183e184 ꢁC; 1H NMR (400 MHz,
CDCl3) d 7.22e7.28 (m, 1H), 7.29e7.40 (m, 4H), 7.40e7.45 (m, 1H),
J¼7.3 Hz, 2H); 13C NMR (75 MHz, CDCl3)
d 111.3, 117.7, 120.3, 123.1,
124.9, 127.2, 127.8, 128.6, 128.6, 129.2, 129.9, 130.5, 130.9, 133.1,
150.7, 154.2.
7.50 (ddd, J¼8.2, 7.2, 1.1 Hz, 1H), 7.53e7.59 (m, 2H), 7.73e7.78 (m,
3H), 8.01 (s, 1H), 8.36 (dd, J¼8.0, 1.7 Hz, 1H); 13C NMR (101 MHz,
4.3.16. 3-(4-Methoxyphenyl)-2-phenylbenzofuran
amorphous solid, 79.7 mg (53%): 1H NMR (400 MHz, CDCl3)
(s, 3H), 6.98e7.05 (m, 2H), 7.23e7.27 (m, 1H), 7.28e7.36 (m, 4H),
7.41e7.45 (m, 2H), 7.50 (d, J¼8.5 Hz, 1H), 7.56 (d, J¼8.2 Hz, 1H), 7.69
(dd, J¼8.2, 1.6 Hz, 2H).
(36).24 Yellow
3.89
CDCl3) d 107.8, 111.5, 118.3, 118.5, 120.5, 123.3, 124.5, 125.0, 125.8,
d
126.7, 127.3, 128.9, 128.9, 130.4, 130.5, 134.1, 153.1, 154.3, 155.4, 156.7,
176.2; HRMS calcd for C23H14O3 [MþH]þ 339.1016, found 339.1015.
4.3.25. 2-Fluoro-4-[7-methoxy-2-(m-tolyl)benzofuran-3-yl]nic-
otinaldehyde (55). Yellow solid, 116.0 mg (65%): mp 177e180 ꢁC; 1H
4.3.17. 3-(3-Methoxyphenyl)-2-phenylbenzofuran (38).7 Yellow oil,
NMR (300 MHz, CDCl3)
d
2.33 (s, 3H), 4.09 (s, 3H), 6.83 (d, J¼7.9 Hz,
125.7 mg (84%): 1H NMR (400 MHz, CDCl3)
d
3.83 (s, 3H), 6.98e7.03
1H), 6.90 (d, J¼8.0 Hz, 1H), 7.19 (t, J¼3.2 Hz, 4H), 7.36 (d, J¼5.1 Hz,
(m, 1H), 7.13 (dd, J¼11.5, 4.9 Hz, 2H), 7.24e7.45 (m, 6H), 7.56e7.63
1H), 7.47 (s, 1H), 8.46 (d, J¼5.1 Hz, 1H), 10.05 (s, 1H); 13C NMR
(m, 2H), 7.75 (dd, J¼8.1, 1.5 Hz, 2H).
(75 MHz, CDCl3)
d 21.7, 56.5, 108.0, 111.5, 124.6, 124.9, 125.2, 125.2,
127.9, 128.9, 129.0, 130.7, 131.0, 139.1, 140.5, 143.6, 145.8, 149.3, 152.3,
152.6, 153.6, 161.4, 164.7, 187.1, 187.1 (extra peaks due to 13Ce19F
coupling); HRMS calcd for C22H16FNO3 [MþH]þ 361.1114, found
362.1187.
4.3.18. 3-(4-Cyanophenyl)-2-phenylbenzofuran (40). Yellow solid,
140.1 mg (98%): mp 113e115 ꢁC, 1H NMR (400 MHz, CDCl3)
d 7.27 (t,
J¼7.5 Hz, 1H), 7.32e7.39 (m, 4H), 7.48 (d, J¼7.7 Hz, 1H), 7.59 (dt,
J¼11.4, 4.6 Hz, 5H), 7.69e7.78 (m, 2H); 13C NMR (100 MHz, CDCl3)
d
111.4, 111.6, 115.9, 118.9, 119.6, 123.6, 125.4, 127.5, 128.9, 129.2,
4.3.26. 2-(4-Acetoxy-3-methoxyphenyl)-5-bromo-3-(3,5-diaceto-
xyphenyl)-7-methoxybenzofuran (59). Compound 59 was synthe-
sized following the general procedure for a three-component
Sonogashira/Cacchi type cyclization and was obtained as a brown
129.3, 130.0, 130.5, 132.9, 138.3, 151.8, 154.3; HRMS calcd for
C21H13NO [MþH]þ 296.107, found 296.1073.
4.3.19. 3-(4-Nitrophenyl)-2-phenylbenzofuran (42).7 Yellow solid,
114.5 mg (73%): mp 135e138 ꢁC; 1H NMR (300 MHz, CDCl3)
amorphous solid (340.6 mg, 60%): 1H NMR (400 MHz, CDCl3)
d 2.29
(s, 6H), 2.31 (s, 3H), 3.67 (s, 3H), 4.03 (s, 3H), 6.95 (s, 1H), 7.00 (s, 1H),
d
7.26e7.28 (m, 1H), 7.32 (d, J¼7.6 Hz, 1H), 7.36e7.39 (m, 4H), 7.52
7.03 (d, J¼8.3 Hz, 1H), 7.09 (d, J¼1.2 Hz, 2H), 7.15 (s, 1H), 7.21 (s, 1H),
(d, J¼7.8 Hz, 1H), 7.60 (d, J¼7.2 Hz, 3H), 7.70 (d, J¼8.2 Hz, 2H), 8.33
(dd, J¼8.7, 1.7 Hz, 2H).
7.35 (d, J¼8.3 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d 20.9, 21.3, 55.9,
56.6, 110.9, 111.0, 111.1, 114.9, 115.6, 115.7, 116.6, 119.8, 120.6, 123.3,
128.2, 132.6, 134.2, 140.4, 142.2, 145.7, 151.2, 151.5, 151.8, 168.9; HRMS
calcd for C28H24BrO9 [MþH]þ 583.0525, found 583.0598.
4.3.20. 3-(2-Nitrophenyl)-2-phenylbenzofuran (44). Yellow crystals,
116.6 mg (74%): mp 119e122 ꢁC; 1H NMR (400 MHz, CDCl3)
d
7.17e7.25 (m, 2H), 7.28e7.39 (m, 4H), 7.51 (dd, J¼7.5, 1.7 Hz, 1H),
4.3.27. 2-(4-Acetoxy-3-methoxyphenyl)-3-(3,5-diacetoxyphenyl)-5-
(1,3-dioxolan-2-yl)-7-methoxybenzofuran (61). Compound 61 was
synthesized following the general procedure for the three-
component Sonogashira/Cacchi type cyclization and was obtained
7.52e7.60 (m, 3H), 7.62 (td, J¼7.7, 1.6 Hz, 1H), 7.68 (td, J¼7.5, 1.5 Hz,
1H), 8.13 (dd, J¼8.0, 1.4 Hz, 1H); 13C NMR (101 MHz, CDCl3)
d 111.6,
113.4, 119.5, 123.5, 125.2, 125.2, 126.9, 128.2, 128.9, 128.9, 129.4,