5124
C. C. Silveira et al. / Tetrahedron Letters 48 (2007) 5121–5124
1997, 536, 233; (d) Miyaev, R. M.; Minkin, V. I. Can. J.
Chem. 1998, 76, 776.
reaction. After this time the mixture was diluted with ethyl
acetate (50 mL) and washed with brine. The organic layer
was separated, dried over MgSO4, and concentrated under
reduced pressure to give an oil, which was purified by
column chromatography (silica gel, hexane/ethyl ace-
tate = 95:5) to give 4. Selected spectral and analytical
5. (a) Leonard, K.; Nelen, M.; Raghu, M.; Detty, M. R. J.
Heterocycl. Chem. 1999, 36, 707–711; (b) Cristau, H. J.;
Chabaud, B.; Labaudiniere, R.; Christol, H. J. Org. Chem.
1986, 51, 875; (c) Stefani, H. A.; Gusevskaya, E. V.;
Comasseto, J. V.; Petragnani, N.; Braga, A. L. Phospho-
rus, Sulfur Silicon Relat. Elem. 1997, 126, 211; (d) Shimizu,
M.; Ando, R.; Kuwajima, I. J. Org. Chem. 1984, 49, 1230;
(e) Testaferri, L.; Tiecco, M.; Tingoli, M.; Chianelli, D.
Tetrahedron 1986, 42, 63; (f) Tiecco, M.; Testaferri, L.;
Tingoli, M.; Chianelli, D.; Montanucci, M. Tetrahedron
Lett. 1984, 25, 4975; (g) Hamaguchi, M.; Nagai, T. J. Org.
Chem. 1989, 54, 3957; (h) Sakakibara, M.; Katsumita, K.;
Watanabe, Y.; Toru, T.; Ueno, Y. Synthesis 1992, 377; (i)
Abe, H.; Fujii, H.; Yamasaki, A.; Kinome, Y.; Takeuchi,
Y.; Harayama, T. Synth. Commun. 2000, 30, 543; (j)
Ogawa, T.; Hayami, K.; Suzuki, H. Chem. Lett. 1989, 769;
(k) Chang, D.; Bao, W. Synthesis 2006, 1786; (l) Wang, Z.;
Mo, H.; Bao, W. Synlett 2007, 91.
6. (a) Ogawa, A.; Obayashi, R.; Ine, H.; Tsuboi, Y.; Sonoda,
N.; Hirao, T. J. Org. Chem. 1998, 63, 881; (b) Ogawa, A.;
Yokohama, H.; Yokohama, K.; Masawaki, T.; Kambe,
N.; Sonoda, N. J. Org. Chem. 1991, 56, 5721; (c) Ogawa,
A.; Yokohama, K.; Obayashi, R.; Han, L. B.; Kambe, N.;
Sonoda, N. Tetrahedron 1993, 49, 1177; (d) Heiba, E. I.;
Dessau, R. M. J. Org. Chem. 1967, 32, 3837.
7. (a) Beletskaya, I.; Moberg, C. Chem. Rev. 2006, 106, 2320;
(b) Ananikov, V. P.; Beletskaya, I. P.; Aleksandrov, G. G.;
Eremenko, I. L. Organometallics 2003, 22, 1414; (c)
Ananikov, V. P.; Beletskaya, I. P. Russ. Chem. Bull.
2004, 53, 561; (d) Ananikov, V. P.; Orlov, N. V.;
Beletskaya, I. P. Russ. Chem. Bull. 2005, 54, 576; (e)
Ananikov, V. P.; Kabeshov, M. A.; Beletskaya, I. P.;
Aleksandrov, G. G.; Eremenko, I. L. J. Organomet. Chem.
2003, 687, 451; (f) Ananikov, V. P.; Beletskaya, I. P. Org.
Biomol. Chem. 2004, 2, 284; (g) Ananikov, V. P.; Maly-
shev, D. A.; Beletskaya, I. P.; Aleksandrov, G. G.;
Eremenko, I. L. J. Organomet. Chem. 2003, 679, 162; (h)
Kuniyasu, H.; Ogawa, A.; Miyazaki, S. I.; Ryu, I.;
Kambe, N.; Sonoda, N. J. Am. Chem. Soc. 1991, 113,
9796; (i) Gareau, Y.; Orellana, A. Synlett 1997, 803.
8. Ogawa, A.; Ogawa, I.; Obayashi, R.; Umezu, K.; Doi, M.;
Hirao, T. J. Org. Chem. 1999, 64, 86.
1
data: Compound 4a: oil; H NMR (400 MHz, CDCl3) d
6.13 (m, 1H), 4.17 (q, J = 7.1 Hz, 2H), 2.79 (t, J = 7.5 Hz,
2H), 2.30 (d, J = 1.12 Hz, 3H), 1.67 (qui, J = 7.2 Hz, 2H),
1.45 (sex, J = 7.2 Hz, 2H), 1.27 (t, J = 7.2 Hz, 3H), 0.93 (t,
J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) d (ppm)
166.62, 157.32, 114.99, 59.55, 31.66, 24.92, 23.09, 22.86,
14.14, 13.35. IR mmax/cmÀ1 1695 (CO), 1584 (C@C);
LRMS m/z (relative intensity) 250 (M++1), 193, 113.
Anal. Calcd for C10H18O2Se: C, 48.20; H, 7.28. Found: C,
48.40, H, 7.46. Compound 4d: mp 45–47 °C; 1H NMR
(400 MHz, CDCl3) d 3.75 (s, 3H), 2.70 (t, J = 7.6 Hz, 2H),
2.5–2.3 (m, 2H), 2.0–1.8 (m, 2H), 1.64 (qui, J = 7.2 Hz,
2H), 1.44 (sext, J = 7.2 Hz, 2H), 1.3–1.2 (m, 3H), 0.93 (t,
J = 7.2, 3H), 0.90 (s, 9H); 13C NMR (100 MHz, CDCl3) d
(ppm) 168.3, 149.5, 123.2, 51.3, 43.4, 33.2, 32.1, 31.6, 29.0,
27.2, 27.0, 24.8, 23.1, 23.1, 13.5; IR mmax/cmÀ1 1682 (CO),
1571 (C@C); LRMS m/z (relative intensity) 332 (M++1),
275, 57. Anal. Calcd for C16H28O2Se: C, 58.00; H, 8.52.
Found: C, 58.24; H, 8.55.
15. (a) Okamura, H.; Miura, M.; Kosugi, K.; Takei, H.
Tetrahedron Lett. 1980, 21, 87–90; (b) Tingoli, M.; Tiecco,
M.; Testaferri, L.; Temperini, A.; Pelizzi, G.; Bacci, A.
Tetrahedron 1995, 51, 4691–4700; (c) Gerard, J.; Hevesi, L.
Tetrahedron 2001, 57, 9109–9121; (d) Tingoli, M.; Tiecco,
M.; Testaferri, L.; Chianelli, D. Gazz. Chim. Ital. 1991,
121, 59–61; (e) Silveira, C. C.; Santos, P. C. S.; Braga, A.
L. Tetrahedron Lett. 2002, 43, 7517; (f) Silveira, C. C.;
Braga, A. L.; Vieira, A. S.; Zeni, G. J. Org. Chem. 2003,
68, 665; (g) Raminelli, C.; Gargalaka, J., Jr.; Silveira, C.
C.; Comasseto, J. V. Tetrahedron Lett. 2004, 45,
4927.
16. General procedure for the synthesis of vinylic vic-bis(aryl-
selenides) 7: To a stirred solution of the organylchalco-
genolate (1.5 mmol, prepared in situ) under argon at
À78 °C was added appropriate enol 6 (1 mmol) in THF
(2 mL). The solution was stirred for 1 h at the same
temperature until completion of the reaction. After this
time the mixture was diluted with ethyl acetate (50 mL)
and washed with brine. The organic layer was separated,
dried over MgSO4, and concentrated under reduced
pressure to give an oil, which was purified by column
chromatography (silica gel, hexane/ethyl acetate = 95:5)
to give 7. Selected spectral and analytical data: Compound
7b: 75–77 °C; 1H NMR (400 MHz, CDCl3) d 7.56 (d,
J = 8.4 Hz, 2H), 7.37–7.20 (m, 7H), 4.13 (q, J = 7.2 Hz,
2H), 2.27 (s, 3H), 1.09 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3) d (ppm) 166.7, 157.4, 137.8, 135.5,
131.9, 130.7, 129.3, 129.0, 128.2, 126.6, 115.8, 61.6, 27.6,
13.8; IR mmax/cmÀ1 1667 (CO), 1571 (C@C); LRMS m/z
(relative intensity) 460 (M++1), 115, 77. Anal. Calcd for
C18H17ClO2Se2: C, 47.13; H, 3.74. Found: C, 46.84; H,
3.84. Compound 7h: mp 114–116 °C; 1H NMR (400 MHz,
CDCl3) d 7.56 (d, J = 8.2 Hz, 2H), 7.32–7.16 (m, 7H), 2.49
(s, 3H), 2.32 (s, 3H); 13C NMR (100 MHz, CDCl3) d
(ppm) 198.9, 164.9, 137.7, 135.5, 132.2, 129.4, 129.3, 129.0,
128.6, 126.3, 121.2, 29.9, 28.4; LRMS m/z (relative
intensity) 430 (M++1), 348, 273, 237, 193, 115, 77. Anal.
Calcd for C17H15ClOSe2: C, 47.63; H, 3.53. Found: C,
47.73; H, 3.32.
9. Silveira, C. C.; Cella, R.; Vieira, A. S. J. Organomet.
Chem. 2006, 691, 5873.
10. Ananikov, V. P.; Kabeshov, M. A.; Beletskaya, I. P.
Synlett 2005, 1015.
11. Yang, D. Y.; Huang, X. Synlett 1997, 891.
12. (a) Perin, G.; Jacob, R. G.; Dutra, L. G.; Azambuja, F.;
Santos, G. F. F.; Lenardao, E. J. Tetrahedron Lett. 2006,
˜
47, 935; (b) Moro, A. V.; Nogueira, C. W.; Barbosa, N. B.
V.; Menezes, P. H.; Rocha, J. B. T.; Zeni, G. J. Org.
Chem. 2005, 70, 5257; (c) Usugi, S. I.; Yorimitsu, H.;
Shinokubo, H.; Oshima, K. Org. Lett. 2004, 6, 601; (d)
Dabdoub, M. J.; Dabdoub, V. B.; Pereira, M. A.
Tetrahedron Lett. 2001, 42, 1595; (e) Truce, W. E.;
Kassinger, R. J. Am. Chem. Soc. 1956, 78, 2748; (f) Back,
T. G.; Bethell, R. J.; Parvez, M.; Wherli, D. J. Org. Chem.
1998, 63, 7908; (g) Truce, W. E.; Goldhamer, D. J. Am.
Chem. Soc. 1959, 81, 5798.
13. Alberdice, M.; Weiler, L.; Sum, F. W. Org. Synth. 1984,
64, 14.
14. General procedure for the synthesis of 4a–f: To a stirred
solution of PhSeLi (1.5 mmol, prepared in situ)17 under
argon at À78 °C was added the appropriate enol 3
(1 mmol) in THF (2 mL). The solution was stirred for
1 h at the same temperature until completion of the
17. Engman, L.; Gupta, V. In Organoselenium Chemistry;
Back, T. G., Ed.; Oxford University Press: Oxford, 1999;
pp 67–91.