P. Sun et al. / Tetrahedron xxx (2013) 1e6
5
128.5, 128.5, 126.2, 120.5, 108.3, 92.0, 88.2, 35.9, 31.4, 30.9, 22.5,
116.5, 111.9, 111.5, 93.1, 88.9, 56.0. MS ESI (m/z): [MþH]þ calcd for
14.0. MS ESI (m/z): [MþH]þ calcd for C21H22, 274.2; found, 274.2.
C17H14O, 234.1; found, 234.1.
4.2.5. (E)-1-Phenyl-4-(4-methoxyphenyl)but-1-en-3-yne.18 Yellow
4.2.14. (E)-1-(3,4-Dimethoxyphenyl)-4-phenylbut-1-en-3-yne.10a
Yellow solid, mp 97e99 ꢀC; 1H NMR (400 MHz, CDCl3) (
, ppm) 7.46
solid, mp 49e50 ꢀC; 1H NMR (400 MHz, CDCl3) (
d, ppm) 7.46e7.37
d
(m, 4H), 7.32 (t, J¼7.1 Hz, 2H), 7.29e7.21 (m, 1H), 6.99 (d, J¼16.2 Hz,
(d, J¼5.9 Hz, 2H), 7.31 (d, J¼6.8 Hz, 3H), 7.00 (d, J¼16.8 Hz, 1H), 6.97
1H), 6.84 (d, J¼8.2 Hz, 2H), 6.37 (d, J¼16.2 Hz, 1H), 3.79 (s, 3H). 13
C
(m, 2H), 6.82 (d, J¼8.1 Hz, 1H), 6.25 (d, J¼16.2 Hz, 1H), 3.90 (s, 3H),
NMR (100 MHz, CDCl3) (d, ppm) 159.5, 136.4, 133.5, 132.9, 128.7,
3.88 (s, 3H). 13C NMR (100 MHz, CDCl3) (
d, ppm) 149.6, 149.0, 141.0,
128.4, 126.1, 115.4, 113.9, 108.3, 91.8, 87.6, 55.2.
131.3, 129.3, 128.3, 128.0, 123.5, 119.9, 111.0, 108.2, 105.9, 91.2, 89.1,
55.8, 55.7.
4.2.6. (E)-1-Phenyl-4-(4-ethoxyphenyl)but-1-en-3-yne.19 Yellow
solid, mp 82e83 ꢀC; 1H NMR (400 MHz, CDCl3) (
, ppm) 7.39 (d,
d
4.2.15. (E)-1-(3,4,5-Trimethoxyphenyl)-4-phenylbut-1-en-3-yne.
J¼8.4 Hz, 4H), 7.32 (t, J¼7.4 Hz, 2H), 7.27 (d, J¼7.1 Hz, 1H), 6.99 (d,
Yellow oil; 1H NMR (400 MHz, CDCl3) (
d, ppm) 7.52e7.44 (m, 2H),
J¼16.2 Hz, 1H), 6.83 (d, J¼8.7 Hz, 2H), 6.37 (d, J¼16.2 Hz, 1H), 4.00
7.40e7.30 (m, 3H), 6.98 (d, J¼16.1 Hz, 1H), 6.66 (s, 2H), 6.31 (d,
(q, J¼7.0 Hz, 2H), 1.39 (t, J¼7.0 Hz, 3H). 13C NMR (75 MHz, CDCl3) (
d,
J¼16.1 Hz,1H), 3.90 (s, 6H), 3.87 (s, 3H). 13C NMR (75 MHz, CDCl3) (
d,
ppm) 158.9, 140.3, 136.4, 132.9, 128.6, 128.4, 126.1, 115.2, 114.4,
108.3, 91.9, 87.5, 63.4, 14.7.
ppm) 153.2, 141.0, 138.6, 131.9, 131.3, 131.1, 128.3, 128.1, 123.3, 107.4,
103.2, 88.7, 60.8, 56.0. MS ESI (m/z): [MþH]þ calcd for C19H18O3,
294.1; found, 294.1.
4.2.7. (E)-1-Phenyl-4-(4-fluorophenyl)but-1-en-3-yne.17 Yellow solid,
mp 83e84 ꢀC; 1H NMR (400 MHz, CDCl3) (
d, ppm) 7.43 (m, 4H), 7.34
4.2.16. (E)-1-(4-Chlorophenyl)-4-phenylbut-1-en-3-yne.17 Yellow
(t, J¼7.3 Hz, 2H), 7.29 (d, J¼7.0 Hz, 1H), 7.05e7.01 (d, J¼15.6 Hz, 1H),
solid, mp 89e90 ꢀC; 1H NMR (300 MHz, CDCl3) (
d, ppm) 7.48e7.45
7.04e6.99 (t, J¼8.8 Hz, 2H), 6.38e6.34 (d, J¼16.4 Hz, 1H). 13C NMR
(m, 2H), 7.38e7.32 (m, 4H), 7.32e7.26 (m, 3H), 6.97 (d, J¼16.2 Hz,
(100 MHz, CDCl3) (
128.9, 128.8, 124.2 (d, JCeF¼6.9 Hz, 2CH), 121.8, 115.0 (d, JCeF¼3.2 Hz,
C), 111.1 (d, JCeF¼22.0 Hz, 2CH), 103.4, 86.1, 84.1.
d
, ppm) 157.9 (d, JCeF¼248.2 Hz, C), 136.8, 131.7,
1H), 6.35 (d, J¼16.2 Hz, 1H). 13C NMR (75 MHz, CDCl3) (
d, ppm)
140.3,135.3,134.7, 132.0,129.4,128.8, 128.8,127.9, 123.7, 109.3, 92.8,
89.1.
4.2.8. (E)-1-Phenyl-4-(4-chlorophenyl)but-1-en-3-yne.11 White solid,
4.2.17. (E)-1-(4-Fluorophenyl)-4-phenylbut-1-en-3-yne.17 White solid,
mp 87e89 ꢀC; 1H NMR (300 MHz, CDCl3) (
d, ppm) 7.43e7.42 (m, 1H),
mp 90e91 ꢀC; 1H NMR (300 MHz, CDCl3) (
d, ppm) 7.54e7.44 (m, 2H),
7.41e7.39 (m, 2H), 7.38e7.33 (m, 3H), 7.30 (t, J¼2.4 Hz, 2H), 7.28e7.27
7.43e7.28 (m, 5H), 7.10e6.93 (m, 2H), 6.99 (d, J¼16.0 Hz, 1H), 6.30 (d,
(m, 1H), 7.04 (d, J¼16.3 Hz, 1H), 6.36 (d, J¼16.2 Hz, 1H). 13C NMR
J¼16.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) (
d, ppm) 163.4 (d,
(75 MHz, CDCl3) (d, ppm) 141.6, 136.1, 134.1, 132.6, 128.7, 128.7, 128.6,
JCeF¼247.6 Hz, C), 140.4, 133.0 (d, JCeF¼3.0 Hz, C), 132.0, 128.8, 128.7,
128.4 (d, JCeF¼8.0 Hz, 2CH), 123.8, 116.2 (d, JCeF¼21.8 Hz, 2CH), 108.4,
92.2, 89.1.
126.3, 121.8, 107.7, 90.5, 89.8.
4.2.9. (E)-1-Phenyl-4-(4-bromophenyl)but-1-en-3-yne.18 White solid,
mp 112e113 ꢀC; 1H NMR (300 MHz, CDCl3) (
d, ppm) 7.47e7.45 (m,
Acknowledgements
2H), 7.44e7.38 (m, 2H), 7.38e7.34 (m, 2H), 7.34e7.23 (m, 3H), 7.12 (d,
J¼16.2 Hz, 1H), 6.35 (d, J¼16.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) (
d
,
We are grateful to the grants from International S&T Co-
operation Program of Jiangsu Province (BZ2010048), the Scientific
Research Foundation for the Returned Overseas Chinese Scholars,
State Education Ministry, the Priority Academic Program De-
velopment of Jiangsu Higher Education Institutions, and the Key
Laboratory of Organic Synthesis of Jiangsu Province.
ppm) 137.2, 131.6, 128.4, 127.1, 124.3, 124.2, 121.8, 117.9, 117.8, 103.2,
86.1, 85.5.
4.2.10. (E)-1-(4-Methylphenyl)-4-phenylbut-1-en-3-yne.17 White
solid, mp 91e93 ꢀC; 1H NMR (300 MHz, CDCl3) (
d, ppm) 7.56e7.41
(m, 2H), 7.41e7.25 (m, 5H), 7.22e7.11 (m, 2H), 7.05 (d, J¼16.4 Hz,
1H), 6.36 (d, J¼16.4 Hz, 1H), 2.38 (s, 3H). 13C NMR (100 MHz, CDCl3)
Supplementary data
(d, ppm) 141.7, 139.2, 134.1, 131.9, 129.9, 128.8, 128.6, 126.7, 124.0,
107.5, 91.9, 89.6, 21.8.
Supplementary data related to this article can be found at http://
4.2.11. (E)-1-(3-Methylphenyl)-4-phenylbut-1-en-3-yne.17 Yellow
oil; 1H NMR (300 MHz, CDCl3) (
d, ppm) 7.55e7.41 (m, 2H),
References and notes
7.38e7.27 (m, 3H), 7.25e7.20 (m, 3H), 7.16e7.07 (m, 1H), 7.01 (d,
J¼16.3 Hz, 1H), 6.37 (d, J¼16.2 Hz, 1H), 2.35 (s, 3H). 13C NMR
(100 MHz, CDCl3) (d, ppm) 141.9, 138.8, 136.7, 132.0, 129.9, 129.1,
128.8, 128.6, 127.5, 123.9, 123.9, 108.3, 92.1, 89.5, 21.9.
~
~
4.2.12. (E)-1-(4-Methoxyphenyl)-4-phenylbut-1-en-3-yne.18 Yellow
solid, mp 97e98 ꢀC; 1H NMR (300 MHz, CDCl3) (
d, ppm) 7.46e7.37
(m, 3H), 7.35e7.25 (m, 4H), 7.00 (d, J¼16.2 Hz,1H), 6.88 (d, J¼7.6 Hz,
2H), 6.24 (d, J¼15.8 Hz, 1H), 3.82 (s, 3H). 13C NMR (75 MHz, CDCl3)
(d, ppm) 160.6, 141.3, 131.9, 129.7, 128.8, 128.5, 128.13, 124.1, 114.7,
9. CuI/PPh3 system for Sonogashira coupling performed in DMF or DMSO, please
106.2, 91.5, 89.7, 55.8.
4.2.13. (E)-1-(3-Methoxyphenyl)-4-phenylbut-1-en-3-yne. Yellow
oil; 1H NMR (300 MHz, CDCl3) (
d, ppm) 7.55e7.44 (m, 3H), 7.41e7.31
(m, 3H), 7.34 (d, J¼15.9 Hz, 1H), 7.29e7.26 (m, 1H), 7.09 (s, 1H), 6.75
(d, J¼8.2 Hz, 1H), 6.35 (d, J¼16.2 Hz, 1H). 13C NMR (100 MHz, CDCl3)
(d, ppm) 156.9, 140.1, 137.3, 134.2, 132.1, 131.9, 128.9, 128.9, 123.6,