Y. Jung, I. Kim / Tetrahedron 68 (2012) 8198e8206
8203
7.15 (t, J¼7.5 Hz, 1H), 6.89 (d, J¼7.5 Hz, 1H), 6.82e6.80 (m, 2H),
4.25e4.15 (m, 2H), 4.09 (t, J¼7.5 Hz,1H), 6.02 (s, 3H), 3.20 (dd, J¼7.0,
17.0 Hz, 1H), 3.07 (dd, J¼8.0, 17.0 Hz, 1H), 1.22 (t, J¼7.5 Hz, 3H); 13C
d
8.60 (d, J¼5.0 Hz, 1H), 7.69 (td, J¼2.0, 8.0 Hz,1H), 7.36 (d, J¼8.0 Hz,
1H), 7.24e7.19 (m, 5H), 4.10 (t, J¼7.5 Hz, 1H), 3.73 (s, 3H), 3.20 (dd,
J¼7.0, 17.0 Hz, 1H), 3.08 (dd, J¼7.0, 17.0 Hz, 1H); 13C NMR (125 MHz,
NMR (125 MHz, CDCl3)
d
171.6, 159.3, 157.4, 149.7, 136.6, 129.3,
CDCl3) d 172.0, 157.1, 149.8, 136.8, 133.9, 132.9, 128.6, 123.3, 122.7,
124.6, 124.2, 123.3, 122.6, 116.6, 114.3, 87.0, 82.3, 61.3, 55.3, 53.1,
122.0, 88.1, 81.3, 52.9, 52.6, 22.5; IR (ATR) 3052, 2947, 2230, 1732,
1588, 1432, 1164, 1084 cmꢁ1; HRMS (ESI) calcd for C17H15ClNO2
300.0791 ([MþH]þ), found 300.0791.
22.5, 14.3; IR (ATR) 3067, 2979, 2835, 1731, 1572, 1469, 1160 cmꢁ1
;
HRMS (FAB) calcd for C19H20NO3 310.1443 ([MþH]þ), found
310.1450.
4.1.15. Methyl 5-(2-acetylphenyl)-2-(pyridin-2-yl)pent-4-ynoate
(5o). Brown gum; 1H NMR (500 MHz, CDCl3)
d
8.60 (d, J¼4.5 Hz,
4.1.9. Ethyl
5-(4-methylcyclohexa-1,5-dien-1-yl)-2-(pyridin-2-yl)
8.59
pent-4-ynoate (5i). Orange gum; 1H NMR (500 MHz, CDCl3)
d
1H), 7.69 (td, J¼2.0, 8.0 Hz, 1H), 7.63 (d, J¼7.5 Hz, 1H), 7.39e7.35 (m,
3H), 7.34e7.31 (m, 1H), 7.23 (dd, J¼5.0, 7.5 Hz, 1H), 4.14 (t, J¼7.5 Hz,
1H), 3.73 (s, 3H), 3.28 (dd, J¼7.0, 17.0 Hz, 1H), 3.18 (dd, J¼8.0,
(d, J¼4.5 Hz, 1H), 7.66 (td, J¼2.0, 8.0 Hz, 1H), 7.37 (d, J¼8.0 Hz, 1H),
7.21e7.18 (m, 3H), 7.05 (d, J¼7.5 Hz, 2H), 4.25e4.15 (m, 2H), 4.08 (t,
J¼7.5 Hz, 1H), 3.19 (dd, J¼7.0, 17.0 Hz, 1H), 3.06 (dd, J¼8.0, 17.0 Hz,
1H), 2.30 (s, 3H), 1.22 (t, J¼7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3)
17.0 Hz, 1H), 2.54 (s, 3H); 13C NMR (125 MHz, CDCl3)
d 200.1, 172.0,
157.0, 149.9, 141.2, 136.9, 134.2, 131.2, 128.4, 128.0, 123.5, 122.8,
121.8, 93.4, 81.3, 52.7, 52.6, 30.1, 22.7; IR (ATR) 3061, 2953, 2856,
1735, 1681, 1590, 1434, 1163 cmꢁ1; HRMS (ESI) calcd for C19H18NO3
308.1287 ([MþH]þ), found 308.1289.
d
171.7, 157.5, 149.7, 137.9, 136.6, 131.5, 129.0, 123.3, 122.5, 120.5,
86.3, 82.4, 61.3, 53.2, 22.6, 21.5, 14.3; IR (ATR) 3049, 2980, 2921,
1732, 1589, 1435, 1159 cmꢁ1; HRMS (FAB) calcd for C19H20NO2
294.1494 ([MþH]þ), found 294.1484.
4.1.16. Methyl 5-(4-acetylphenyl)-2-(pyridin-2-yl)pent-4-ynoate
4.1.10. Ethyl 2-(pyridin-2-yl)-5-(thiophen-2-yl)pent-4-ynoate
(5p). White solid, mp: 71.9e73.0 ꢀC; 1H NMR (500 MHz, CDCl3)
(5j). Yellow gum; 1H NMR (500 MHz, CDCl3)
d
8.59 (d, J¼4.0 Hz,
d
8.60 (d, J¼4.0 Hz, 1H), 7.84 (d, J¼7.0 Hz, 2H), 7.70 (td, J¼1.5, 7.5 Hz,
1H), 7.67 (td, J¼1.0, 7.5 Hz, 1H), 7.36 (d, J¼7.5 Hz, 1H), 7.20 (ddd,
J¼1.0, 5.0, 7.0 Hz, 1H), 7.15 (dd, J¼1.0, 5.0 Hz, 1H), 7.04 (d, J¼3.5 Hz,
1H), 6.89 (dd, J¼3.5, 5.0 Hz,1H), 4.25e4.15 (m, 2H), 4.08 (t, J¼7.5 Hz,
1H), 3.23 (dd, J¼7.5, 17.0 Hz, 1H), 3.09 (dd, J¼7.5, 17.0 Hz, 1H), 1.22 (t,
1H), 7.38e7.35 (m, 3H), 7.25e7.22 (m,1H), 4.12 (t, J¼8.0 Hz,1H), 3.74
(s, 3H), 3.25 (dd, J¼7.0,17.0 Hz,1H), 3.12 (dd, J¼8.0,17.0 Hz,1H), 2.57
(s, 3H); 13C NMR (125 MHz, CDCl3)
d 197.4, 171.9, 157.0, 149.8, 136.8,
136.0,131.7,128.5,128.2,123.3,122.7, 90.9, 81.8, 52.8, 52.6, 26.7, 22.5;
J¼7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3)
d
171.5, 157.2, 149.7, 136.7,
IR (ATR) 3070, 2998, 2927, 2223, 1734, 1678, 1588, 1436, 1172 cmꢁ1
;
131.4, 126.8, 126.3, 123.7, 123.3, 122.6, 91.2, 75.5, 61.4, 52.9, 22.8,
14.3; IR (ATR) 3076, 2980, 2933, 1730, 1588, 1434, 1160 cmꢁ1; HRMS
(FAB) calcd for C16H16NO2S 286.0902 ([MþH]þ), found 286.0905.
HRMS (ESI) calcd for C19H18NO3 308.1287 ([MþH]þ), found 308.1297.
4.1.17. Methyl 5-(2-cyanophenyl)-2-(pyridin-2-yl)pent-4-ynoate
(5q). Brown gum; 1H NMR (500 MHz, CDCl3)
d
8.60 (d, J¼4.0 Hz,
1H), 7.70 (td, J¼2.0, 7.5 Hz, 1H), 7.58 (d, J¼7.5 Hz, 1H), 7.48 (td, J¼1.5,
8.0 Hz,1H), 7.45 (d, J¼7.5 Hz,1H), 7.40 (d, J¼7.5 Hz,1H), 7.34 (td, J¼1.0,
7.5 Hz, 1H), 7.22 (ddd, J¼1.0, 5.0, 8.0 Hz, 1H), 4.17 (dd, J¼7.0, 8.0 Hz,
1H), 3.75 (s, 3H), 3.33 (dd, J¼7.0, 17.0 Hz, 1H), 3.18 (dd, J¼8.0, 17.0 Hz,
4.1.11. Ethyl 2-(pyridin-2-yl)-5-(pyridin-3-yl)pent-4-ynoate
(5k). Yellow gum; 1H NMR (500 MHz, CDCl3)
d
8.60 (d, J¼5.0 Hz,
1H), 8.51 (d, J¼1.0 Hz, 1H), 8.47 (dd, J¼1.5, 5.0 Hz, 1H), 7.69 (td,
J¼1.5, 8.0 Hz, 1H), 7.57 (dt, J¼2.0, 8.0 Hz, 1H), 7.37 (d, J¼8.0 Hz, 1H),
7.22 (ddd, J¼1.0, 5.0, 7.5 Hz, 1H), 7.18 (dd, J¼5.0, 8.0 Hz, 1H),
4.26e4.16 (m, 2H), 4.10 (t, J¼7.5 Hz, 1H), 3.23 (dd, J¼7.0, 17.0 Hz,
1H), 3.12 (dd, J¼8.0, 17.0 Hz, 1H), 1.23 (t, J¼7.0 Hz, 3H); 13C NMR
1H);13CNMR(125 MHz, CDCl3)
d171.8, 156.8, 149.8,137.0, 132.6,132.6,
132.5,132.3,128.0,127.4,123.8,122.7,117.7,115.2, 94.4, 78.7, 52.6, 52.5,
22.55; IR (ATR) 3067, 2952, 2229, 1735,1590,1434,1163 cmꢁ1; HRMS
(ESI) calcd for C18H15N2O2 291.1134 ([MþH]þ), found 291.1136.
(125 MHz, CDCl3)
d 171.5, 157.2, 152.5, 149.8, 148.3, 138.5, 136.7,
123.3, 123.0, 122.7, 120.7, 90.9, 79.1, 61.4, 52.9, 22.5, 14.3; IR (ATR)
3049, 2980, 2934, 2226, 1731, 1588, 1473, 1161 cmꢁ1; HRMS (FAB)
calcd for C17H17N2O2 281.1290 ([MþH]þ), found 281.1280.
4.1.18. 2-(Pyridin-2-yl)-5-(pyridin-3-yl)pent-4-ynenitrile
(5r). Yellow gum; 1H NMR (400 MHz, CDCl3)
d
8.64 (d, J¼2.8 Hz,
1H), 8.58 (s, 1H), 8.51 (d, J¼3.2 Hz, 1H), 7.78 (td, J¼1.2, 7.6 Hz, 1H),
7.66 (d, J¼8.0 Hz, 1H), 7.56 (d, J¼7.6 Hz, 1H), 7.32 (t, J¼7.5 Hz, 1H),
7.24 (t, J¼8.0 Hz, 1H), 4.29 (t, J¼6.4 Hz, 1H), 3.26 (dd, J¼6.4,
17.2 Hz, 1H), 3.19 (dd, J¼7.2, 16.8 Hz, 1H); 13C NMR (100 MHz,
4.1.12. Methyl 5-phenyl-2-(pyridin-2-yl)pent-4-ynoate (5l). Brown
solid, mp: 51.2e53.7 ꢀC; 1H NMR (500 MHz, CDCl3)
d 8.59 (d,
J¼4.5 Hz, 1H), 7.67 (t, J¼7.5 Hz, 1H), 7.37 (d, J¼8.0 Hz, 1H), 7.29e7.27
(m, 2H), 7.24e7.19 (m, 4H), 4.11 (t, J¼8.0 Hz, 1H), 3.73 (s, 3H), 3.21
(dd, J¼7.0, 17.0 Hz, 1H), 3.09 (dd, J¼8.5, 17.0 Hz, 1H); 13C NMR
CDCl3)
d 153.4, 152.5, 150.2, 148.8, 137.4, 123.6, 122.3, 120.0,
118.9, 87.7, 81.1, 39.3, 24.9; IR (ATR) 3051, 2922, 2246, 1588,
1435 cmꢁ1; HRMS (ESI) calcd for C15H12N3 234.1031 ([MþH]þ),
found 234.1021.
(125 MHz, CDCl3)
d 172.1, 157.3, 149.8, 136.7, 131.6, 128.2, 127.9,
123.5, 123.4, 122.6, 87.0, 82.4, 53.0, 52.5, 22.5; IR (ATR) 3033, 2954,
2113, 1736, 1589, 1434, 1172 cmꢁ1; HRMS (ESI) calcd for C17H16NO2
266.1181 ([MþH]þ), found 266.1181.
4.1.19. Methyl 4-(4-cyano-4-(pyridin-2-yl)but-1-yn-1-yl)benzoate
(5s). Yellow solid, mp: 88.4e89.9 ꢀC; 1H NMR (400 MHz, CDCl3)
d
8.65 (d, J¼4.0 Hz,1H), 7.95 (d, J¼8.4 Hz, 2H), 7.78 (td, J¼2.0, 8.0 Hz,
4.1.13. Methyl 5-(4-fluorophenyl)-2-(pyridin-2-yl)pent-4-ynoate
(5m). Yellow gum; 1H NMR (500 MHz, CDCl3)
d
8.61 (d, J¼4.0 Hz,
1H), 7.56 (d, J¼7.6 Hz, 1H), 7.42 (d, J¼8.4 Hz, 2H), 7.32 (ddd, J¼0.8,
4.8, 7.6 Hz, 1H), 4.29 (t, J¼6.4 Hz, 1H), 3.19 (s, 3H), 3.25 (dd, J¼6.0,
16.8 Hz, 1H), 3.18 (dd, J¼7.6, 16.8 Hz, 1H); 13C NMR (100 MHz,
1H), 7.69 (td, J¼2.0, 8.0 Hz, 1H), 7.36 (d, J¼8.0 Hz, 1H), 7.27e7.22 (m,
3H), 6.94 (t, J¼8.5 Hz, 2H), 4.10 (t, J¼8.0 Hz, 1H), 3.74 (s, 3H), 3.20
(dd, J¼7.0, 17.0 Hz, 1H), 3.07 (dd, J¼8.0, 17.0 Hz, 1H); 13C NMR
CDCl3)
d 166.6, 153.5, 150.2, 137.4, 131.8, 129.7, 129.5, 127.5, 123.6,
122.3, 119.0, 87.3, 83.7, 52.4, 39.4, 25.0; IR (ATR) 3064, 2952, 2237,
1705, 1590, 1436, 1280 cmꢁ1; HRMS (ESI) calcd for C18H15N2O2
291.1134 ([MþH]þ), found 291.1120.
(125 MHz, CDCl3)
d 172.1, 163.3, 161.3, 157.2, 149.8, 136.8, 133.5,
133.4, 123.4, 122.7, 119.6, 115.6, 115.4, 86.7, 81.3, 53.0, 52.6, 22.5; IR
(ATR) 3056, 2952, 1736, 1590, 1505, 1434, 1218, 1155 cmꢁ1; HRMS
(ESI) calcd for C17H15FNO2 284.1087 ([MþH]þ), found 284.1090.
4.1.20. 2-(Pyridin-2-yl)-5-(3-(trifluoromethyl)phenyl)pent-4-
ynenitrile (5t). Yellow gum; 1H NMR (500 MHz, CDCl3)
d
8.64 (d,
4.1.14. Methyl 5-(4-chlorophenyl)-2-(pyridin-2-yl)pent-4-ynoate
(5n). Yellow solid, mp: 81.8e83.9 ꢀC; 1H NMR (500 MHz, CDCl3)
J¼4.5 Hz, 1H), 7.77 (t, J¼7.5 Hz, 1H), 7.60 (s, 1H), 7.56e7.53 (m, 3H),