10154
F. Yang et al. / Tetrahedron 67 (2011) 10147e10155
763, 1154, 1345, 1738, 2918 cmꢁ1; HRMS (EI) calcd for C23H19I2NO2S
(neat): 692, 759, 1367, 1738, 3023 cmꢁ1; HRMS (EI) calcd for
(m/z): 626.9226, found: 626.9211.
C23H17BrINO2S (m/z): 576.9208; found, 576.9215.
4.5.10. 4,5-Diiodo-6-phenyl-1-tosyl-1,2,3,6-tetrahydropyridine
4.5.18. 3,4-Diiodo-2-phenylthiophene (13a). Slight yellow solid; 1H
(4c). White solid; 1H NMR (400 MHz, CDCl3)
d
7.75e7.72 (m, 2H),
NMR (500 MHz, CDCl3)
d
7.62 (1H, s), 7.54e7.52 (2H, m), 7.46e7.39
92.7, 93.5, 128.4, 128.9, 129.0,
7.41e7.73 (m, 7H), 5.86 (s, 1H), 3.63e3.59 (m, 1H), 3.21e3.13 (m,
(3H, m); 13C NMR (125 MHz, CDCl3)
d
1H), 2.58e2.55 (m, 2H), 2.47 (s, 3H); 13C NMR (100 MHz, CDCl3)
129.4, 134.8; IR (neat): 692, 764, 862, 1092, 1210, 1270, 1441, 1464,
1597, 1739, 2923 cmꢁ1; HRMS (ESI) calcd for C10H6I2S (m/z):
411.8280, found: 411.8281.
d
21.6, 39.3, 39.9, 67.2, 107.6, 109.4, 127.0, 128.4, 128.5, 128.7, 129.7,
136.3, 137.0, 143.8; IR (neat): 726, 961, 1154, 1345, 1738,
2918 cmꢁ1; HRMS (EI) calcd for C18H17I2NO2S (m/z), 564.9070;
found, 564.9077.
4.5.19. 3,4-Diiodo-2-p-tolylthiophene (13b). Slight yellow solid; 1H
NMR (500 MHz, CDCl3)
d
7.59 (1H, s), 7.43 (2H, d, J¼8.0 Hz), 7.25
4.5.11. 4,5-Diiodo-6-phenyl-3,6-dihydro-2H-thiopyran (6n). Yellow
(2H, d, J¼8.0 Hz), 2.42 (3H, s); 13C NMR (125 MHz, CDCl3)
d 21.3,
solid; 1H NMR (400 MHz, CDCl3)
d
7.39e7.30 (m, 3H), 7.26e7.24 (m,
2H), 4.88 (s, 1H), 3.27e3.22 (m, 2H), 2.85e2.79 (m, 1H), 2.60e2.55
(m, 1H); 13C NMR (100.40 MHz, CDCl3)
24.8, 44.5, 53.8, 109.78,
92.4, 93.4, 128.76, 129.1, 129.3, 131.9, 138.9, 144.2; IR (neat): 742,
814, 864, 1217, 1367, 1469, 1738, 2919 cmꢁ1; HRMS (ESI) calcd for
C11H8I2S (m/z): 425.8436, found: 425.8436.
d
114.2, 127.5, 127.7, 128.4, 140.6; IR (neat): 694, 1069, 1450, 1583,
2920 cmꢁ1; HRMS (EI) calcd for C11H10I2S (m/z): 427.8593; found,
427.8583.
4.5.20. 2-(4-Chlorophenyl)-3,4-diiodothiophene (13c). Slight yellow
solid; 1H NMR (300 MHz, CDCl3)
d
7.62 (1H, s), 7.47 (2H, d, J¼9.0 Hz),
7.41 (2H, d, J¼9.0 Hz); 13C NMR (75 MHz, CDCl3)
d 93.3, 93.7, 128.7,
4.5.12. 3,4-Diiodo-2-phenyl-1-tosyl-1H-pyrrole (11a). Yellow solid;
129.2, 130.7, 133.2, 135.0, 142.7; IR (neat): 735, 818, 1012, 1093, 1217,
1366, 1463, 1738, 2924 cmꢁ1; HRMS (ESI) calcd for C10H5ClI2S (m/z):
445.7890, found: 445.7893.
1H NMR (300 MHz, CDCl3)
d
7.63 (s, 1H), 7.38e7.33 (m, 1H),
7.29e7.23 (m, 2H), 7.15e7.05 (m, 4H), 6.99e6.96 (m, 2H), 2.32 (s,
3H); 13C NMR (75.45 MHz, CDCl3)
21.6, 78.0, 85.5, 127.0, 127.5,
d
127.6, 129.3, 129.6, 130.5, 131.9, 134.5, 136.6, 145.5; IR (neat): 695,
661, 765, 1085, 1171, 1366, 3144 cmꢁ1; HRMS (EI) calcd for
C17H13I2NO2S, 548.8649 (m/z): found, 548.8643.
4.5.21. 3,4-Diiodo-2-methyl-5-phenylthiophene (13d). Slight yellow
oil; 1H NMR (300 MHz, CDCl3)
d
7.54e7.50 (2H, m), 7.46e7.38 (3H,
m), 2.60 (3H, s); 13C NMR (75 MHz, CDCl3)
d
20.2, 92.3, 96.1, 128.3,
128.6, 129.4, 135.1, 139.7, 141.1; IR (neat): 691, 761, 821, 1031, 1216,
1375, 1599, 1739, 2921 cmꢁ1; HRMS (ESI) calcd for C11H8I2S (m/z):
425.8436, found: 425.8440.
4.5.13. 3,4-Diiodo-2-p-tolyl-1-tosyl-1H-pyrrole (11b). White solid;
1H NMR (400 MHz, CDCl3)
d
7.73 (s, 1H), 7.31e7.12 (m, 6H),
7.00e6.98 (m, 2H), 2.48 (m, 3H), 2.44 (m, 3H); 13C NMR
(100.40 MHz, CDCl3) 21.5, 21.7, 78.1, 85.5, 126.8, 127.5, 127.5, 128.2,
129.4, 131.6, 134.4, 136.7, 139.2, 145.3; IR (neat): 664, 1174, 1372,
1725, 2918 cmꢁ1
HRMS (EI): calcd for C18H15I2NO2S (m/z):
d
4.5.22. (E)-S-2,3-Diiodo-4-oxo-4-phenylbut-2-enyl
(14a). Brown oil; 1H NMR (400 MHz, CDCl3)
7.94e7.91 (m, 2H),
7.63e7.59 (m, 1H), 7.50e7.46 (m, 2H), 4.35 (s, 2H), 2.42 (s, 3H); 13C
NMR (100 MHz, CDCl3) 30.3, 46.5, 95.0, 96.2, 129.0, 130.3, 131.1,
ethanethioate
d
;
562.8913; found, 562.8911.
d
134.2, 191.3, 193.1; IR (neat): 618, 703, 1124, 1232, 1665, 1693, 1737,
2970 cmꢁ1; HRMS (EI): [MþH]þ calcd for C12H11I2O2S, 472.8569;
found, 472.8553.
4.5.14. 2-(4-Bromophenyl)-3,4-diiodo-1-tosyl-1H-pyrrole
(11c). White solid; 1H NMR (400 MHz, CDCl3)
d
7.72 (s, 1H), 7.51 (d,
J¼8.0 Hz, 2H), 7.30e7.20 (m, 4H), 7.96 (d, J¼8.0 Hz, 2H), 2.45 (s, 3H);
13C NMR (100.40 MHz, CDCl3)
21.7, 78.3, 86.0, 123.9, 127.3, 127.5,
d
Supplementary data
129.4, 129.7, 130.8, 133.4, 134.3, 135.2, 145.7; IR (neat): 663, 1169,
1372, 1593, 3134 cmꢁ1; HRMS (EI) calcd for C17H12BrI2NO2S (m/z):
626.7862; found, 626.7858.
Supplementary data associated with this article can be found, in
4.5.15. (E)-3,4-Diiodo-2-styryl-1-tosyl-1H-pyrrole
solid; 1H NMR (400 MHz, CDCl3)
(11d). White
7.70 (d, J¼8.0 Hz, 2H), 7.64 (s,
d
References and notes
1H), 7.53 (d, J¼8.0 Hz, 2H), 7.46e7.35 (m, 3H), 7.30e7.25 (m, 3H),
7.14 (d, J¼16.0 Hz, 1H); 2.42 (s, 3H); 13C NMR (100.40 MHz, CDCl3)
1. For selected reviews, see: (a) Biehl, E. R. Prog. Heterocycl. Chem. 2011, 22, 109; (b)
Cicch, S.; Cordero, F. M.; Giomi, D. Prog. Heterocycl. Chem. 2011, 22, 308.
2. (a) Wu, C.; Decker, E. R.; Blok, N.; Bui, H.; You, T. J.; Wang, J.; Bourgoyne, A. R.;
Knowles, V.; Berens, K. L.; Holland, G. W.; Brock, T. A.; Dixon, R. A. F. J. J. Med.
d
21.7, 81.0, 82.4, 116.1, 126.5, 126.9, 127.4, 128.4, 128.7, 129.9, 133.6,
134.6, 135.9, 136.0, 145.7; IR (neat): 663, 1173, 1378, 1738,
3146 cmꢁ1; HRMS (EI) calcd for C19H15I2NO2S (m/z): 574.8913;
found, 574.8917.
€
Chem. 2004, 47, 1969; (b) Furstner, A. Angew. Chem., Int. Ed. 2003, 43, 3582; (c)
Modica, M.; Santagati, M.; Guccione, S.; Russo, F.; Cagnotto, A.; Goegan, M.;
Mennini, T. Eur. J. Med. Chem. 2000, 35, 1065; (d) Lipshutz, B. H. Chem. Rev. 1986,
86, 795; (e) Montagnon, T.; Tofi, M.; Vassilikogiannakis, G. Acc. Chem. Res. 2008,
41, 1001.
4.5.16. 3,4-Diiodo-2,5-diphenyl-1-tosyl-1H-pyrrole
(11e). White
€
3. (a) Mishra, A.; Ma, C.-Q.; Peter Bauerle, P. Chem. Rev. 2009, 109, 1141; (b) Yoon,
solid; 1H NMR (400 MHz, CDCl3)
d 7.42e7.24 (m, 10H), 7.09 (d,
Z. S.; Kwon, J. H.; Yoon, M.-C.; Koh, M. K.; Noh, S. B.; Sessler, J. L.; Lee, J. T.; Seidel,
D.; Aguilar, A.; Shimizu, S.; Suzuki, M.; Osuka, A.; Kim, D. J. Am. Chem. Soc. 2006,
128, 14128; (c) Lee, J.-S.; Kang, N.-Y.; Kim, Y. K.; Samanta, A.; Feng, S.; Kim, H. K.;
Vendrell, M.; Park, J. H.; Chang, Y.-T. J. Am. Chem. Soc. 2009, 131, 10077; (d)
Funahashi, M.; Zhang, F.; Tamaoki, N. Adv. Mater. 2007, 19, 353; (e) Koumura, N.;
Wang, Z.-S.; Mori, S.; Miyashita, M.; Suzuki, E.; Hara, K. J. Am. Chem. Soc. 2006,
J¼8.0 Hz, 2H), 7.04 (d, J¼8.0 Hz, 2H), 2.38 (s, 3H); 13C NMR
(100.40 MHz, CDCl3)
d 21.7, 87.6, 127.3, 127.4, 128.9, 129.3, 131.5,
132.7, 135.0, 139.1, 145.1; IR (neat): 692, 758, 1172, 1366, 1738,
3023 cmꢁ1; HRMS (EI) calcd for C23H17I2NO2S (m/z): 624.9049;
found, 624.9070.
ꢁ
128, 14256; (f) Murphy, A. R.; Liu, J.; Luscombe, C.; Kavulak, D.; Frechet, J. M. J.;
Kline, R. J.; McGehee, M. D. Chem. Mater. 2005, 17, 4892.
4. (a) Nakamura, I.; Yamamoto, Y. Chem. Rev. 2004, 104, 2127; (b) Yamamoto, Y. J.
Org. Chem. 2007, 72, 7817; (c) Patil, N. T.; Yamamoto, Y. Chem. Rev. 2008, 108,
3395; (d) Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004, 104, 3079; (e)
Deiters, A.; Martin, S. F. Chem. Rev. 2004, 104, 2199; (f) Zeni, G.; Larock, R. C.
Chem. Rev. 2004, 104, 2285; (g) Yet, L. Chem. Rev. 2000, 100, 2963.
4.5.17. 3-Bromo-4-iodo-2,5-diphenyl-1-tosyl-1H-pyrrole
(11e0). White solid; 1H NMR (400 MHz, CDCl3)
d 7.44e7.37 (m,10H),
7.10 (d, J¼8.0 Hz, 2H), 7.04 (d, J¼8.0 Hz, 2H), 2.38 (s, 3H); 13C NMR
(100.40 MHz, CDCl3)
d 21.7, 82.5, 112.4, 127.2, 127.4, 127.5, 128.9,
5. For reviews, see: (a) Larock, R. C. In Acetylene Chemistry. Chemistry, Biology, and
Material Science; Diederich, F., Stang, P. J., Tykwinski, R. R., Eds.; Wiley-VCH:
129.0, 129.2, 130.9, 131.2, 131.4, 132.2, 134.9, 135.2, 138.8, 145.1; IR