X.-B. Shao et al. / Tetrahedron xxx (2018) 1e8
5
CDCl3):
d
¼ 131.7, 128.5, 128.4, 123.4, 89.5 ppm.
d
¼ 7.57e7.50 (m, 3H), 7.36e7.27 (m, 4H), 7.14e7.07 (m, 2H) ppm.
13C NMR (100 MHz, CDCl3):
d
¼ 162.8 (d, J ¼ 250.2 Hz), 133.6, 131.8,
4.4.3. 1-Methyl-3-(phenylethynyl)benzene(4ca) [7m]
130.1 (d, J ¼ 8.1 Hz), 128.7, 128.5, 124.1 (d, J ¼ 3.6 Hz), 123.03, 115.7
(d, J ¼ 20.8 Hz), 94.6, 82.8 ppm.
Yield: 0.092 g (96%), yellow oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.53e7.51 (m, 2H), 7.35e7.31 (m, 5H), 7.22 (t, J ¼ 7.6 Hz, 1H), 7.13
(t, J ¼ 8.0 Hz, 1H), 2.33 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3):
4.4.12. 1,3-Difluoro-5-(phenylethynyl)benzene(4la) [7n]
d
¼ 138.1, 132.3, 131.7, 130.2, 129.7, 129.3, 128.8, 128.44, 128.36,
Yield: 0.103 g (96%), white solid, m.p. 38e39 ꢀC. 1H NMR
128.3, 123.5, 123.2, 89.7, 89.2, 21.4 ppm.
(400 MHz, CDCl3):
7.04e7.02 (m, 3H), 6.89e6.76 (m, 1H) ppm. 13C NMR (100 MHz,
CDCl3):
126.0, 123.9, 122.3, 115.6e115.4 (m), 114.6e114.4 (m), 106.0 (t,
J ¼ 25.2 Hz), 104.4 (t, J ¼ 25.3 Hz), 91.3, 87.1 ppm.
d
¼ 7.53e7.51 (m, 2H), 7.37e7.35 (m, 2H),
4.4.4. 1-Ethyl-4-(phenylethynyl)benzene(4da) [7n]
d
¼ 162.8 (dd, J1 ¼ 247.4 Hz, J2 ¼ 13.4 Hz), 131.7, 128.9, 128.4,
Yield: 0.072 g (70%), yellow oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.60e7.51 (m, 2H), 7.46e7.42 (m, 2H), 7.35e7.29 (m, 3H),
7.22e7.14 (m, 2H), 2.68e2.62 (q, J ¼ 6.6 Hz, 2H), 1.23 (t, J ¼ 7.6 Hz,
3H) ppm. 13C NMR (100 MHz, CDCl3):
d
¼ 144.8, 132.6, 131.7 (d,
4.4.13. 1-Bromo-3-(phenylethynyl)benzene(4ma) [7c]
J ¼ 3.6 Hz), 128.9, 128.4, 128.2, 128.0, 127.3, 123.6, 120.5, 89.7, 88.8,
Yield: 0.127 g (99%), yellow oil. 1H NMR (400 MHz, CDCl3):
¼ 7.67 (s, 1H), 7.52e7.50 (m, 2H), 7.44e7.41 (m, 2H), 7.33e7.32 (m,
29.0, 15.5 ppm.
d
3H), 7.16 (t, J ¼ 8.0 Hz,1H) ppm. 13C NMR (100 MHz, CDCl3):
4.4.5. 1-(phenylethynyl)-4-propylbenzene(4ea) [7g]
d
¼ 134.2, 131.6, 131.3, 130.1, 129.7, 128.6, 128.3, 125.2, 122.7, 122.1,
Yield: 0.072 g (66%), yellow oil. 1H NMR (400 MHz, CDCl3):
90.7, 87.8 ppm.
d
¼ 7.60e7.51 (m, 2H), 7.45e7.43 (m, 2H), 7.35e7.28 (m, 3H),
7.16e7.12 (m, 2H), 2.58 (t, J ¼ 7.6 Hz, 2H), 1.68e1.59 (m, 2H), 0.93 (t,
4.4.14. 1-Bromo-4-(phenylethynyl)benzene(4na) [7f]
J ¼ 7.2 Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3):
d
¼ 143.3, 132.5,
Yield: 0.0570 g (44%), white solid, m.p.: 83e84 ꢀC. 1H NMR
131.6 (d, J ¼ 5.3 Hz), 128.9, 128.7, 128.7, 128.4, 128.2, 127.4, 127.3,
(400 MHz, CDCl3):
d
¼ 7.53e7.51 (m, 2H), 7.48e7.45 (m, 2H),
123.6, 120.5, 89.7, 88.9, 38.1, 24.5, 13.9 ppm.
7.39e7.33 (m, 5H) ppm. 13C NMR (100 MHz, CDCl3):
d
¼ 133.2, 131.7
(d, J ¼ 2.1 Hz), 128.6, 128.5, 127.3, 123.1, 122.6, 122.4, 90.6, 88.4 ppm.
4.4.6. 1-Pentyl-4-(phenylethynyl)benzene(4fa) [7e]
Yield: 0.083 g (66%), yellow oil. 1H NMR (400 MHz, CDCl3):
4.4.15. 1-Chloro-4-(phenylethynyl)benzene(4oa) [7f]
d
¼ 7.53e7.50 (m, 2H), 7.45e7.41 (m, 2H), 7.35e7.27 (m, 3H),
Yield: 0.058 g (55%), white solid, m.p.: 79e81 ꢀC. 1H NMR
7.15e7.11 (m, 2H), 2.61e2.56 (m, 2H), 1.64e1.56 (m, 2H), 1.34e1.27
(400 MHz, CDCl3):
d
¼ 7.53e7.51 (m, 2H), 7.46e7.44 (d, J ¼ 8.4 Hz,
(m, 4H), 0.90e0.87 (m, 3H) ppm. 13C NMR (100 MHz, CDCl3):
2H), 7.35e7.30 (m, 5H) ppm. 13C NMR (100 MHz, CDCl3):
d
¼ 134.4,
d
¼ 143.5, 132.5, 131.7, 131.6, 128.9, 128.7, 128.6, 128.4, 128.2, 127.3,
132.9, 131.7, 128.8, 128.6, 128.5, 123.1, 121.9, 90.5, 88.4 ppm.
123.6, 120.5, 89.7, 88.8, 36.0, 31.6, 31.1, 22.7, 14.2 ppm.
4.4.16. 1-(phenylethynyl)-4-(trifluoromethyl)benzene(4pa) [7e]
Yield: 0.117 g (95%), white solid, m.p.: 95e96 ꢀC. 1H NMR
4.4.7. 1-(tert-butyl)-4-(phenylethynyl)benzene(4ga) [7f]
Yield: 0.083 g (71%), white solid, m.p. 55e59 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
¼ 7.65e7.59 (m, 4H), 7.58e7.54 (m, 2H),
(400 MHz, CDCl3):
d
¼ 7.60e7.51 (m, 2H), 7.48e7.41 (m, 2H),
7.39e7.34 (m, 3H). 13C NMR (100 MHz, CDCl3):
d
¼ 131.93, 131.89,
7.36e7.27 (m, 5H), 1.31 (s, 9H). 13C NMR (100 MHz, CDCl3):
130.0(q, J ¼ 32.4 Hz), 128.9, 128.6, 127.3, 125.4 (q, J ¼ 3.8 Hz), 124.1
d
¼ 151.6, 132.4, 131.7, 131.5, 128.9, 128.4, 128.2, 127.3, 125.6, 125.5,
(q, J ¼ 270.6 Hz), 122.7, 91.8, 88.1 ppm.
123.6, 120.3, 89.7, 88.7, 34.9, 31.3 ppm.
4.4.17. 2-(phenylethynyl)thiophene(4qa) [7k]
4.4.8. 1-Methoxy-4-(phenylethynyl)benzene(4ha) [7e]
Yield: 0.078 g (85%), yellow oil. 1H NMR (400 MHz, CDCl3):
Yield: 0.069 g (67%), white solid, m.p.: 79e81 ꢀC. 1H NMR
d
¼ 7.58 (d, J ¼ 7.6 Hz, 1H), 7.52e7.49 (m, 2H), 7.45e7.41 (t,
(400 MHz, CDCl3):
d
¼ 7.52e7.46 (m, 4H), 7.29e7.34 (m, 3H), 6.86
J ¼ 7.2 Hz, 1H), 7.36e7.30 (m, 3H), 6.99 (t, J ¼ 4.0 Hz, 1H) ppm. 13
C
(d, J ¼ 10.8 Hz, 2H), 3.80 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3):
NMR (100 MHz, CDCl3):
d
¼ 132.0,131.5, 128.9,128.53,128.50,127.4,
d
¼ 159.7, 133.2, 131.6, 128.4, 128.1, 123.7, 115.4, 114.1, 89.5, 88.2,
127.3, 127.2, 123.4, 123.0, 93.2, 82.8 ppm.
55.4 ppm.
4.4.18. 1-(phenylethynyl)naphthalene(4ra) [7m]
4.4.9. 1-Fluoro-4-(phenylethynyl)benzene(4ia) [7e]
Yield: 0.094 g (85%), yellow oil. 1H NMR (400 MHz, CDCl3):
Yield: 0.089 g (90%), white solid, m.p.: 104e108 ꢀC. 1H NMR
d
¼ 8.44 (d, J ¼ 8.0 Hz, 1H), 7.83e7.74 (m, 3H), 7.65e7.63 (d,
(400 MHz, CDCl3):
d
¼ 7.53e7.49 (m, 4H), 7.35e7.34 (m, 3H),
J ¼ 6.8 Hz, 2H), 7.59e7.56 (t, J ¼ 7.2 Hz, 1H), 7.51e7.48 (t, J ¼ 7.6 Hz,
7.06e7.01 (m, 2H) ppm. 13C NMR (100 MHz, CDCl3):
d
¼ 162.6 (d,
1H), 7.43e7.34 (m, 4H) ppm. 13C NMR (100 MHz, CDCl3):
133.3, 131.8, 130.5, 128.9, 128.5, 128.5, 128.4, 126.9, 126.5, 126.3,
125.9, 123.5, 121.0, 94.5, 87.7 ppm.
d
¼ 133.4,
J ¼ 248.2 Hz),134.7(d, J ¼ 8.6 Hz), 133.6(d, J ¼ 8.3 Hz), 131.7, 128.5 (d,
J ¼ 3.9 Hz), 123.2, 116.1(d, J ¼ 22.2 Hz), 115.8(d, J ¼ 20.0 Hz), 89.2,
88.4 ppm.
4.4.19. 2-(p-tolylethynyl)thiophene(4ab)
4.4.10. 1-Fluoro-3-(phenylethynyl)benzene(4ja) [7h]
Yield: 0.063 g (64%), white solid, m.p.: 59e61 ꢀC. 1H NMR
Yield: 0.085 g (86%), white solid, m.p. 28e30 ꢀC. 1H NMR
(400 MHz, CDCl3):
d
¼ 7.42 (d, J ¼ 8.0 Hz, 2H), 7.27 (d, J ¼ 4.4 Hz,
(400 MHz, CDCl3):
7.23e7.18 (m, 1H), 7.06e7.00 (m, 1H) ppm. 13C NMR (100 MHz,
CDCl3):
d
¼ 7.53e7.51 (m, 2H), 7.34e7.26 (m, 5H),
2 H), 7.16 (d, J ¼ 8.0 Hz, 2H), 7.00 (t, J ¼ 4.4 Hz, 1H), 2.37 (s, 3H) ppm.
13C NMR (100 MHz, CDCl3):
d
¼ 138.7, 131.8,131.4, 129.3,127.2, 127.1,
d
¼ 162.5 (d, J ¼ 245.0 Hz), 131.8, 130.0 (d, J ¼ 8.7 Hz), 128.7,
123.6, 119.9, 93.3, 82.1, 21.7 ppm. HRMS (ESI) m/z calcd for C13H11Sþ
(MþH)þ 199.05760, found 199.05775.
128.5, 127.6 (d, J ¼ 3.0 Hz), 125.2 (d, J ¼ 9.5 Hz), 122.9, 118.5 (d,
J ¼ 22.6 Hz) 115.7 (d, J ¼ 21.1 Hz), 90.4, 88.2 (d, J ¼ 3.4 Hz) ppm.
4.4.20. 2-(m-tolylethynyl)thiophene(4cb)
4.4.11. 1-Fluoro-2-(phenylethynyl)benzene(4ka) [7d]
Yield: 0.060 g (61%), yellow oil. 1H NMR (400 MHz, CDCl3):
Yield: 0.063 g (65%), colourless oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.34e7.31 (m, 2H), 7.28e7.21 (m, 3H), 7.14 (d, J ¼ 7.6 Hz, 1H),
Please cite this article in press as: X.-B. Shao, et al., Highly efficient synthesis of 1,2-disubstituted acetylenes derivatives from the cross-coupling