M.-Y. Chang et al. / Tetrahedron Letters 52 (2011) 826–829
829
1990, 31, 5449; (f) Hodgson, D. M.; Arif, T. J. Am. Chem. Soc. 2008, 130, 16500;
(g) Shao, L. X.; Shi, M. Synlett 2006, 1269; (h) Wang, Y.; Lam, H. W. J. Org. Chem.
2009, 74, 1353; (i) Wei, H.-X.; Jasoni, R. L.; Hu, J.; Li, G.; Pare, P. W. Tetrahedron
2004, 60, 10233; (j) Li, W.; Li, J.; Wan, Z.-K.; Wu, J.; Massefski, W. Org. Lett.
2007, 9, 4607.
3. Conclusion
In summary, a one-step novel synthetic methodology for pro-
ducing a series of vinyl halides by the Selectfluor- or NXS-mediated
reaction was presented in this Letter. For a skeleton with endo-ole-
fin or exo-olefin, the bromination priority with different equiva-
lents was well-investigated. Several structures of the target
products were confirmed by X-ray crystal analysis. Further studies
on the biological evaluation of the available compounds are ac-
tively underway in laboratories.
6. (a) Stavber, S.; Sotler-Pecan, T.; Zupan, M. Tetrahedron 1994, 50, 12235; (b)
Stavber, S.; Sotler-Pecan, T.; Zupan, M. Bull. Chem. Soc. Jpn. 1996, 69, 169; (c)
Stavber, S.; Zupan, M.; Poss, A. J.; Shia, G. A. Tetrahedron Lett. 1995, 36, 6769.
7. (a) Nyffeler, P. T.; Duron, S. G.; Burkart, M. D.; Vincent, S. P.; Wong, C. H. Angew.
Chem., Int. Ed. 2005, 44, 192; (b) France, S.; Weatherwax, A.; Lectka, T. Eur. J. Org.
Chem. 2005, 475; (c) Singh, R. P.; Shreeve, J. M. Acc. Chem. Res. 2004, 37, 31; (d)
Ma, J.-A.; Cahard, D. Chem. Rev. 2004, 104, 6119; (e) Banks, R. E. J. Fluorine Chem.
1998, 87, 1; (f) Shimizu, M.; Hiyama, T. Angew. Chem., Int. Ed. 2005, 44, 214; (g)
Pihko, P. M. Angew. Chem., Int. Ed. 2006, 45, 544; (h) Uneyama, K. Organofluorine
Chemistry, 1st ed.; Blackwell Publishing Ltd: Oxford, 2006.
Acknowledgments
8. Silveira, C. C.; Braga, A. L.; Kaufman, T. S.; Lenardao, E. J. Tetrahedron 2004, 60,
8295.
9. (a) Jensen, B. L.; Slobodzian, S. V. Tetrahedron Lett. 2000, 41, 6029; (b) Alcock, N.
J.; Mann, I.; Peach, P.; Wills, M. Tetrahedron: Asymmetry 2002, 13, 2485; (c)
Nichols, D. E.; Cassady, J. M.; Persons, P. E.; Yeung, M. C.; Clemens, J. A. J. Med.
Chem. 1989, 32, 2128.
The authors would like to thank the National Science Council of
the Republic of China for its financial support (NSC 99-2113-M-
037-006-MY3). The project is also supported by a grant from the
Kaohsiung Medical Research Foundation (KMU-Q099003).
10. A representative synthetic transformation of skeleton 2 from 1 is as follows:
Selectfluor or NXS (1.05 mmol) was added to
a solution of skeleton 1
(1.0 mmol) in acetonitrile or methanol (10 mL) at rt. The reaction mixture
was stirred at rt for 2–3 h. Saturated sodium bicarbonate solution (2 mL) was
added to the reaction mixture and the solvent was concentrated. The residue
was extracted with ethyl acetate (3 ꢀ 20 mL). The combined organic layers
were washed with brine, dried, filtered, and evaporated to afford crude
product. Purification on silica gel (hexane/AcOEt = 10:1–6:1) afforded 2. For
compound 2a: mp = 95–96 °C; HRMS (ESI, M++1) calcd for C18H18FO2 285.1291,
found 285.1293; 1H NMR (400 MHz): d 7.27–7.24 (m, 2H), 6.99–6.95 (m, 2H),
6.77 (d, J = 8.8 Hz, 1H), 6.75 (d, J = 2.8 Hz, 1H), 6.62 (dd, J = 2.8, 8.8 Hz, 1H), 3.86
References and notes
1. For vinyl fluorides: (a) van Steenis, J. H.; van der Gen, A. J. Chem. Soc., Perkin
Trans. 1 2002, 2117. and references cited herein; (b) Shen, Y. J. Organomet.
Chem. 2006, 691, 1452; For vinyl chlorides, bromides: (c) Li, W.; Li, J.; Wan, Z.-
K.; Wu, J.; Massefski, W. Org. Lett. 2007, 9, 4607. and references cited herein; (d)
Ye, C.; Shreeve, J. M. J. Org. Chem. 2004, 69, 8561; For vinyl selenides: (e) Perin,
G.; Lenardao, E. J.; Jacob, R. G.; Panatieri, R. B. Chem. Rev. 2009, 109, 1277.
2. (a) Grossma, G.; Poncioni, M.; Bornand, M.; Jolivet, B.; Neuburger, M.; Sequin, U.
Tetrahedron 2003, 59, 3237; (b) Thibonnet, J.; Vu, V. A.; Berillon, L.; Knochel, P.
Tetrahedron 2002, 58, 4787; (c) Pravst, I.; Zupan, M.; Stavber, S. Curr. Org. Chem.
2009, 13, 47.
3. (a) Chang, M.-Y.; Hsu, R.-T.; Tseng, T.-W.; Sun, P.-P.; Chang, N. C. Tetrahedron
2004, 60, 5545; (b) Sun, P.-P.; Chang, M.-Y.; Chiang, M.-Y.; Chang, N.-C. Org.
Lett. 2003, 5, 1761; (c) Gutke, H.; Braun, N. A.; Spitzner, D. Tetrahedron 2004, 60,
8137; (d) Bellur, E.; Langer, P. Eur. J. Org. Chem. 2005, 4815; (e) Veisi, H.;
Ghorbani-Vaghei, R. Tetrahedron 2010, 66, 7445.
4. (a) Sciotti, R. J.; Pliushchev, M.; Wiedeman, P. E.; Balli, D.; Flamm, R.; Nilius, A.
M.; Marsh, K.; Stolarik, D.; Jolly, R.; Ulrich, R.; Djuric, S. W. Bioorg. Med. Chem.
Lett. 2002, 12, 2121; (b) Han, S.-Y.; Inoue, H.; Terada, T.; Kamoda, S.; Saburi, Y.;
Sekimata, K.; Saito, T.; Kobayashi, M.; Shinozaki, K.; Yoshida, S.; Asami, T.
Bioorg. Med. Chem. Lett. 2002, 12, 1139; (c) Bohlmann, R. J. Fluorine Chem. 1992,
58, 192; (d) Asakura, N.; Usuki, Y.; Iio, H.; Tanaka, T. J. Fluorine Chem. 2006, 127,
808; (e) Yin, B.; Wang, L.; Inagi, S.; Fuchigami, T. Tetrahedron 2010, 66, 6820; (f)
Crenshaw, M. D.; Zimmer, H. J. Med. Chem. 1983, 48, 2782; (g) Turner, R. T.;
Evans, G. L.; Sluka, J. P.; Adrian, M. D.; Bryant, H. U.; Turner, C. H.; Sato, M.
Endocrinology 1998, 139, 3712; (h) Sneader, W. Drug Discovery 2005, 255.
5. (a) Romagnoli, R.; Baraldi, P. G.; Tabrizi, M. A.; Bermejo, J.; Estevez, F.; Borgatti,
M.; Gambari, R. J. Med. Chem. 2005, 48, 7906; (b) Beria, I.; Baraldi, P. G.; Cozzi,
P.; Caldarelli, M.; Geroni, C.; Marchini, S.; Mongelli, N.; Romagnoli, R. J. Med.
Chem. 2004, 47, 2611; (c) Mattews, D. P.; Waid, P. P.; Sabol, J. S.; McCarthy, J. R.
Tetrahedron Lett. 1994, 35, 5177; (d) Marhold, M.; Buer, A.; Hiemstra, H.; van
Maarseveen, J. H.; Haufe, G. Tetrahedron Lett. 2004, 45, 57; (e) McCarthy, J. R.;
Matthews, D. P.; Edwards, M. L.; Stemerick, D. M.; Jarvi, E. T. Tetrahedron Lett.
(s, 3H), 3.79 (s, 3H), 3.04 (dt, J = 2.4, 8.4 Hz, 2H), 2.67 (dt, J = 5.6, 8.4 Hz, 2H); 13
C
NMR (100 MHz): d 158.76, 157.79 (d, J = 49.2 Hz), 154.90, 134.66, 131.20 (2ꢀ),
128.19 (d, J = 5.3 Hz), 127.69, 126.30 (d, J = 7.6 Hz), 125.97, 116.21 (d,
J = 13.7 Hz), 113.80, 113.74 (2ꢀ), 110.85, 55.21, 29.04 (d, J = 6.8 Hz), 25.25 (d,
J = 25.0 Hz). Anal. Calcd for C18H17FO2: C, 76.04; H, 6.03. Found: C, 76.43; H,
6.32.
11. CCDC 784042 (2a), 789504 (2c), 789886 (2f), 776260 (2g), 790221 (2h), and
789691 (2m) contain the supplementary crystallographic data for this paper.
12. (a) Chang, M.-Y.; Wu, T.-C.; Lin, C.-Y.; Hung, C.-Y. Tetrahedron Lett. 2006, 47,
8347; (b) Rhoden, J. B.; Bouvet, M.; Izenwasser, S.; Wade, D.; Lomenzo, S. A.;
Trudell, M. L. Bioorg. Med. Chem. 2005, 13, 5623; (c) Lindsley, C. W.; Zhao, Z.;
Leister, W. H.; O’Brien, J.; Lemaire, W.; Williams, D. L., Jr.; Chen, T.-B.; Chang, R.
S. L.; Burno, M.; Jacobson, M. A.; Sur, C.; Kinney, G. G.; Pettibone, D. J.; Tiller, P.
R.; Smith, S.; Tsou, N. N.; Duggan, M. E.; Conn, P. J.; Hartman, G. D.
ChemMedChem 2006, 1, 807.
13. Chang, M.-Y.; Lin, C.-H.; Chen, Y.-L.; Hsu, R.-T.; Chang, C.-Y. Tetrahedron Lett.
2010, 51, 3154.
14. CCDC 789892 (8a), 772680 (9), and 772681 (10) contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge
Union Road, Cambridge CB2 1EZ, UK; fax: 44-1223-336033; e-mail: http://