5980
Y. Kuninobu et al. / Tetrahedron 64 (2008) 5974–5981
1416.03, 1376.92, 742.05, 705.57, 649.55; HRMS (ESI) calcd for
C
4.4.18. 2-Formylthiophene-3-carboxylic acid phenylamide (16b)
1H NMR (400 MHz, CDCl3) d 7.17 (t, J¼7.5 Hz, 1H), 7.39 (t,
J¼7.8 Hz, 2H), 7.78 (d, J¼7.8 Hz, 2H), 7.85 (d, J¼4.8 Hz, 1H), 7.94 (d,
J¼4.8 Hz,1H), 9.99 (s, 1H), 10.87 (br, 1H); 13C NMR (100 MHz, CDCl3)
d 120.3, 120.4, 124.7, 129.1, 134.2, 135.0, 137.9, 142.1, 174.8, 183.8; IR
(Nujol, n/cmꢂ1) 3328, 3097, 1659, 1598, 1539, 1514, 1443, 1419, 1316,
21H18OSNa ([MþNa]þ): 341.0976, found: 341.0934.
4.4.11. 3-(3-Formylthiophen-2-yl) propionic acid ethyl ester (12a)
1H NMR (400 MHz, CDCl3) d 1.25 (t, J¼7.2 Hz, 3H), 2.74 (t,
J¼7.2 Hz, 2H), 3.51 (t, J¼7.2 Hz, 2H), 4.14 (q, J¼7.2 Hz, 2H), 7.13 (d,
J¼5.4 Hz, 1H), 7.39 (d, J¼5.4 Hz, 1H), 10.04 (s, 1H); 13C NMR
(100 MHz, CDCl3) d 14.2, 23.4, 35.8, 60.8, 123.4, 128.0, 137.0, 171.7,
184.6, 185.6; IR (Nujol, n/cmꢂ1) 2980, 1732, 1681, 1520, 1446, 1374,
1234,1181,1043, 725; HRMS (ESI) calcd for C10H12O3SNa ([MþNa]þ):
235.0405, found: 235.0429.
1260, 1205, 906, 772; HRMS (ESI) calcd for
C12H9NO2SNa
([MþNa]þ): 254.0252, found: 254.0203.
4.4.19. 4-Formyl-5-methylthiophene-3-carboxylic acid
phenylamide (16c)
1H NMR (400 MHz, CDCl3) d 2.88 (s, 3H), 7.13 (t, J¼7.8 Hz, 1H),
7.37 (t, J¼7.8 Hz, 2H), 7.79 (d, J¼7.8 Hz, 2H), 8.21 (s, 1H), 11.64 (s,
1H); 13C NMR (100 MHz, CDCl3) d 14.8, 120.4, 124.2, 128.9, 131.8,
132.0, 137.8, 138.5, 159.2, 160.1, 186.6; IR (Nujol, n/cmꢂ1) 1653, 1559,
4.4.12. 3-(2-Formyl-thiophen-3-yl) propionic acid ethyl ester (12b)
1H NMR (400 MHz, CDCl3) d 1.22 (t, J¼7.2 Hz, 3H), 2.75 (t,
J¼7.5 Hz, 2H), 3.30 (t, J¼7.5 Hz, 2H), 4.12 (q, J¼7.2 Hz, 2H), 7.05 (d,
J¼4.5 Hz, 1H), 7.66 (d, J¼4.5 Hz, 1H), 10.06 (s, 1H); 13C NMR
(100 MHz, CDCl3) d 14.1, 23.6, 35.1, 60.7, 130.5, 134.6, 138.1, 149.5,
172.0, 182.2; IR (Nujol, n/cmꢂ1) 1731, 1660, 1427, 1393, 1373, 1241,
1190,1096,1041, 752; HRMS (ESI) calcd for C10H12O3SNa ([MþNa]þ):
235.0405, found: 235.0385.
1456, 1377, 1193, 763; HRMS (ESI) calcd for
C13H11NO2SNa
([MþNa]þ): 268.0408, found: 268.0379.
4.4.20. 3-Formylthiophene-2-carboxylic acid (4-trifluoro-
methylphenyl) amide (16d)
1H NMR (400 MHz, CDCl3) d 7.61–7.67 (m, 4H), 7.92 (d, J¼8.4 Hz,
4.4.13. 3-(4-Formyl-2,5-dimethylthiophen-3-yl) propionic acid
ethyl ester (12c)
2H), 9.96 (s, 1H); 13C NMR (100 MHz, CDCl3) d 120.1, 126.2, 126.3,
126.3,130.8,134.8,135.2, 141.0,148.6,158.1,187.7; IR (Nujol, n/cmꢂ1
)
1H NMR (400 MHz, CDCl3) d 1.22 (t, J¼7.2 Hz, 3H), 2.31 (s, 3H),
2.51 (t, J¼7.7 Hz, 2H), 2.69 (s, 3H), 3.06 (t, J¼7.7 Hz, 2H), 4.09 (q,
J¼7.2 Hz, 2H), 10.05 (s, 1H); 13C NMR (100 MHz, CDCl3) d 12.3, 13.6,
22.3, 34.5, 60.3, 131.2, 134.5, 135.9, 151.4, 173.1, 185.2; IR (Nujol, n/
cmꢂ1) 1734, 1675, 1558, 1457, 1375, 1297, 125, 1172, 1101, 1037;
HRMS (ESI) calcd for C12H16O3SNa ([MþNa]þ): 263.0718, found:
263.0682.
1675, 1619, 1602, 1554, 1504, 1430, 1412, 1319, 1254, 1158, 1122,
1106, 1073, 1008, 846. Anal. Calcd for C13H8F3NS: C, 52.17; H, 2.69;
N, 4.68. Found: C, 52.00; H, 2.95; N, 4.57.
4.4.21. 3-Formylthiophene-2-carboxylic acid (4-methoxyphenyl)
amide (16e)
1H NMR (400 MHz, CDCl3) d 3.81 (s, 3H), 6.91 (d, J¼9.0 Hz, 2H),
7.58–7.61 (m, 2H), 7.73 (d, J¼9.0 Hz, 2H), 9.95 (s, 1H), 11.90 (s, 1H);
13C NMR (100 MHz, CDCl3) d 55.4, 114.1, 121.8, 129.8, 131.0, 134.4,
135.0, 149.6, 156.5, 157.4, 187.4; IR (Nujol, n/cmꢂ1) 1875, 1674, 1644,
1565, 1504, 1402, 1278, 1241, 1193, 1170, 1124, 1111, 1029, 857, 828,
800, 714; HRMS (ESI) calcd for C13H11NO3SNa ([MþNa]þ): 284.0357,
found: 284.0303.
4.4.14. 3-(2-Formyl-1-methyl-1H-pyrrol-3-yl) propionic acid ethyl
ester (12d)
1H NMR (400 MHz, CDCl3) d 1.25 (t, J¼7.1 Hz, 3H), 2.62 (t, J¼7.8 Hz,
2H), 3.08 (t, J¼7.8 Hz, 2H), 3.90 (s, 3H), 4.13 (q, J¼7.1 Hz, 2H), 6.03 (d,
J¼2.4 Hz,1H), 6.75 (d, J¼2.4 Hz,1H), 9.76 (s,1H); 13C NMR (100 MHz,
CDCl3) d 14.2, 20.9, 35.8, 36.9, 60.5, 109.2, 127.7, 131.1, 137.3, 172.6,
178.2; IR (Nujol, n/cmꢂ1) 1734, 1657, 1507, 1461, 1376, 1184; HRMS
(ESI) calcd for C11H15NO3Na ([MþNa]þ): 232.0950; found: 232.0908.
4.4.22. 3-Formylthiophene-2-carboxylic acid (2-methoxyphenyl)
amide (16f)
1H NMR (400 MHz, CDCl3) d 3.98 (s, 3H), 6.94 (d, J¼8.1 Hz, 1H),
7.00 (t, J¼7.8 Hz,1H), 7.12 (t, J¼7.8 Hz,1H), 7.55 (d, J¼5.4 Hz,1H), 7.59
4.4.15. 3-(3-Oxo-pentyl) thiophene-2-carbaldehyde (12e)
1H NMR (400 MHz, CDCl3) d 1.06 (t, J¼7.3 Hz, 3H), 2.44 (q,
J¼7.3 Hz, 2H), 2.85 (t, J¼7.4 Hz, 2H), 3.46 (t, J¼7.4 Hz, 2H), 7.11 (d,
J¼5.3 Hz, 1H), 7.38 (d, J¼5.3 Hz, 1H), 10.05 (s, 1H); 13C NMR
(100 MHz, CDCl3) d 7.7, 22.1, 36.0, 43.4, 123.2, 128.0, 136.7, 155.3,
184.7, 209.1; IR (Nujol, n/cmꢂ1) 1714, 1676, 1519, 1457, 1411, 1387,
1234, 1114, 730; HRMS (ESI) calcd for C10H12O2SNa ([MþNa]þ):
219.0546, found: 219.0444.
(d, J¼5.4 Hz,1H), 8.47 (d, J¼8.1 Hz,1H),10.06 (s,1H),11.33 (s,1H); 13
C
NMR (100 MHz, CDCl3) d 55.8, 110.4, 120.9, 121.4, 124.8, 127.3, 129.6,
133.1, 136.5, 148.2, 149.3, 158.1, 186.5; IR (Nujol, n/cmꢂ1) 3120, 3086,
2769,1683,1633,1603,1542,1508,1427,1402,1332,1266,1224,1193,
1179, 1164, 1129, 1030, 931, 822, 802, 771, 746; HRMS (ESI) calcd for
C
13H11NO3SNa ([MþNa]þ): 284.0357, found: 284.0331.
4.4.23. 3-Formylthiophene-2-carboxylic acid phenethylamide (16g)
1H NMR (400 MHz, CDCl3) d 2.97 (t, J¼7.5 Hz, 2H), 3.69–3.74 (m,
2H), 7.21–7.34 (m, 5H), 7.51 (d, J¼5.1 Hz, 1H), 7.54 (d, J¼5.1 Hz, 1H),
9.69 (br, 1H), 9.90 (s, 1H); 13C NMR (100 MHz, CDCl3) d 35.4, 41.4,
126.4, 128.5, 128.7, 129.3, 133.6, 135.8, 138.8, 148.0, 160.0, 186.8; IR
(Nujol, n/cmꢂ1) 3254, 3117, 1674, 1615, 1556, 1515, 1307, 1225, 1195,
819. Anal. Calcd for C14H13NO2S: C, 64.84; H, 5.05; N, 5.40. Found: C,
65.11; H, 5.26; N, 5.41.
4.4.16. 2-tert-Butyl-3,5-dimethyl-2,2a,6,6a-tetrahydro-4-thia-2-
azacyclobuta[a]pentalen-1-one (13)
1H NMR (400 MHz, CDCl3) d 1.32 (s, 9H), 2.21 (s, 3H), 2.40 (s, 3H),
2.53 (ddd, J¼1.2, 10.2, 16.8 Hz, 1H), 2.92 (dd, J¼1.2, 16.8 Hz, 1H), 4.05
(ddd, J¼2.4, 4.2, 10.2 Hz, 1H), 4.57 (d, J¼4.2 Hz, 1H); 13C NMR
(100 MHz, CDCl3) d 13.0,14.7, 24.5, 28.3, 53.3, 53.7, 58.7,126.9,129.7,
140.3, 145.1, 169.9; IR (Nujol, n/cmꢂ1) 1716, 1458, 1376, 1294, 1260,
1229, 1192, 1129, 1084, 1013, 843, 729; HRMS (ESI) calcd for
C
14H19NOSNa ([MþNa]þ): 272.1085, found: 272.1082.
4.4.24. 3-Formylthiophene-2-carboxylic acid cyclohexyl-
amide (16h)
4.4.17. 3-Formylthiophene-2-carboxylic acid phenylamide (16a)
1H NMR (400 MHz, CDCl3) d 7.15 (t, J¼7.5 Hz,1H), 7.37 (t, J¼7.5 Hz,
2H), 7.58 (s, 2H), 7.79 (d, J¼7.5 Hz, 2H), 9.93 (s, 1H); 13C NMR
(100 MHz, CDCl3) d 120.4,124.6,129.0,130.1,134.4,135.2,137.9,149.3,
157.8, 187.4; IR (Nujol, n/cmꢂ1) 1671, 1646, 1624, 1559, 1540, 1404,
1322, 1273, 1245, 1189, 1120, 1013, 691. Anal. Calcd for C12H9N2S: C,
62.32; H, 3.92; N, 6.06. Found: C, 62.04; H, 4.03; N, 6.09.
1H NMR (400 MHz, CDCl3) d 1.26–2.01 (m, 10H), 3.96 (br, 1H),
7.52 (d, J¼5.4 Hz, 1H), 7.56 (d, J¼5.1 Hz, 1H), 9.61 (br, 1H), 9.95 (s,
1H); 13C NMR (100 MHz, CDCl3) d 24.5, 25.6, 31.5, 32.6, 48.7, 129.0,
133.7, 135.6, 138.9, 186.9; IR (Nujol, n/cmꢂ1) 3285, 3083, 1678, 1619,
1544, 1514, 1348, 1322, 1257, 1241, 1229, 1151, 1137, 1096, 924, 824,
792. Anal. Calcd for C12H15N2S: C, 60.73; H, 6.37; N, 5.90. Found: C,
60.43; H, 6.46; N, 5.68.