The first representatives of the novel 4,7а-dihydro-3аН-thiopyrano[3,4-d]isoxazole heterocyclic system, containing an ester, carboxyl, or hydroxymethyl group at position 3 and a trifluoromethyl group at position 6 were obtained by [3+2] cycloaddition reaction of ethyl cyanocarboxylate N-oxide and 6-trifluoromethyl-2Н-thiopyran, followed by further transformations of the ethyl 6-trifluoromethyl-4,7а-dihydro-3аН-thiopyrano[3,4-d]isoxazole-3-carboxylate intermediate. The cleavage of the isoxazoline ring of the obtained compounds led to the formation of 6-trifluoromethyl-2Н-thiopyran derivatives with nitrile or carbonyl-containing functionality at position 3. Transformations of the thiopyran moiety in 4,7а-dihydro-3аН-thiopyrano[3,4-d]isoxazole were studied for the case of Pummerer reaction product with oxidized sulfur atom, ethyl 6-trifluoromethyl-4,7а-dihydro-3аН-thiopyrano[3,4-d]isoxazole-3-carboxylate 5-oxide, which was converted to ethyl 6-trifluoromethyl-4Н-thiopyrano[3,4-d]isoxazole-3-carboxylate.
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References
Nagireddy, J. R.; Raheem, M.-A.; Haner, J.; Tam. W. Curr. Org. Synth. 2011, 8, 659.
Koroleva, E. V.; Lakhvich, F. A. Russ. Chem. Rev. 1997, 66, 27. [Usp. Khim. 1997, 66, 31.]
Konopíková, M.; Fišera, L.; Šturdik, E.; Ujhélová, R.; Varkondá, Š.; Hýblová, O. Chem. Pap. 1991, 45, 775.
Kwon, T.; Heiman, A. S.; Oriaku, E. T.; Yoon, K.; Lee, H. J. J. Med. Chem. 1995, 38, 1048.
Hwang, I. T.; Kim, H. R.; Jeon, D. J.; Hong, K. S.; Song, J. H.; Cho, K. Y. J. Agric. Food Chem. 2005, 53, 8639.
Arai, M. A.; Kuraishi, M.; Arai, T.; Sasai, H. Chirality 2003, 15, 101.
Belen’kii, L. I. In Nitrile Oxides, Nitrones, and Nitronates in Organic Synthesis. Novel Strategies in Synthesis; 2nd ed.; Feuer, H., Ed.; Wiley: Hoboken, 2008, Ch. 1, p. 1.
(a) Gakh, A. A., Shermolovich, Yu. G. Curr. Top. Med. Chem. 2014, 14, 952. (b) Fluorinated Heterocyclic Compounds: Synthesis, Chemistry, and Applications; Petrov, A. V., Ed.; Wiley: Hoboken, 2009. (c) Fluorine in Heterocyclic Chemistry; Nenajdenko, V., Ed.; Springer, 2014.
(a) Siry, S. A.; Timoshenko, V. M. Tetrahedron Lett. 2010, 51, 6406. (b) Siry, S. A.; Timoshenko, V. M. Tetrahedron Lett. 2011, 52, 6260.
Kozikowsky, A. P.; Adamczyk, M. J. Org. Chem. 1983, 48, 366.
Caldirola, P.; De Amici, M.; De Micheli, C. Heterocycles 1985, 23, 2479.
(a) Torssell, K. B. G.; Hazell, A. C.; Hazell, R. G. Tetrahedron 1985, 41, 5569. (b) Campbell, M. M.; Cosford, N. D. P.; Rae, D. R.; Sainsbury, M. J. Chem. Soc., Perkin Trans. 1 1991, 765. (c) Lathbury, D. C.; Parsons, P. J. J. Chem. Soc., Chem. Commun. 1982, 291. (d) Jedlovská, E.; Fišera, L. Chem. Pap. 1991, 45, 419.
Siry, S. A.; Timoshenko, V. M.; Bouillon, J.-P. J. Fluorine Chem. 2012, 137, 6.
Hass, W.; König, W. A. Liebigs Ann. Chem. 1982, 1615.
Caldirola, P.; De Amici, M.; De Micheli, C.; Wade, P. A.; Price, D. T.; Bereznak, J. F. Tetrahedron 1982, 42, 5267.
Karpaviciene, I.; Lapinskaite, R.; Brukstus, A.; Cikotiene, I. Synlett 2012, 381.
Clerici, F.; Gelmi, M. L.; Soave, R.; Valle, M. Tetrahedron 1998, 54, 11285.
Hwang, S. H.; Kurth, M. J. Tetrahedron Lett. 2002, 43, 53.
O’Connor, D. E.; Lyness, W. I. J. Am. Chem. Soc. 1963, 85, 3044.
O’Connor, D. E.; Lyness, W. I. J. Am. Chem. Soc. 1964, 86, 3840.
Craig, D.; Daniels, K.; MacKenzie, A. R. Tetrahedron 1993, 49, 11263.
Siry, S. A.; Timoshenko, V. M.; Vlasenko, Yu. G.; Baranova, G. V.; Zagorodnya, S. D.; Nesterova, N. V. Chem. Heterocycl. Compd. 2014, 50, 467. [Khim. Geterotsikl. Soedin. 2014, 513.]
Shimizu, H.; Kudo, N.; Kataoka, T.; Hori, M. J. Chem. Soc., Perkin Trans. 1 2001, 2269.
Heras, M.; Gulea, M.; Masson, S.; Philouze, C. Eur. J. Org. Chem. 2004, 160.
(а) Fischer, W. Helv. Chim. Acta. 1991, 74, 1119. (b) Ramadas, S. R.; Vijaya Krishna, M. Phosphorus, Sulfur Silicon Relat. Elem. 1983, 15, 311. (c) Ramalingam, K.; Thyvelikakath, G. X.; Darrell Berlin, K.; Chesnut, R. W.; Brown, R. A.; Durham, N. N.; Ealick, S. E.; Van der Helm, D. J. Med. Chem. 1977, 20, 847.
(a) Fravolini, A.; Schiaffella, F.; Strappaghetti, G. J. Heterocycl. Chem. 1979, 16, 29. (b) Cecchetti, V.; Fravolini, A.; Fringuelli, R.; Schiaffella, F. Heterocycles 1984, 22, 2293. (c) Cecchetti, V.; Fravolini, A.; Schiaffella, F. J. Heterocycl. Chem. 1982, 19, 1045.
Chang, R. K.; Kim, K. Tetrahedron Lett. 2000, 41, 8499.
King, G. S.; Magnus, P. D.; Rzepa, H. S. J. Chem. Soc., Perkin Trans. 1 1972, 437.
Azarifar, D.; Khosravi, K.; Veisi, R.-A. ARKIVOC 2010, (ix), 178.
Sizov, A. Yu.; Kovregin, A. N.; Serdyuk, R. N.; Vorob’ev, M. V.; Porosyatnikov, V. A.; Tsvetkov, A. A.; Korneev, D. O.; Ermolov, A. F. Russ. Chem. Bull. 2006, 55, 1200. [Izv. Akad. Nauk, Ser. Khim. 2006, 1156.]
Watkin, D. J.; Prout, C. K.; Carruthers, J. R.; Betteridge, P. W. CRYSTALS, Issue 10; Chemical Crystallography Laboratory, University of Oxford: Oxford, 1996.
Sheldrick, G. Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, A64, 112.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, 2015, 51(7), 630–638
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The Supplementary Information file containing 1H, 13C NMR spectra and selected X-ray data of the synthesized compounds is available for authorized users.
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Siryi, S.A., Timoshenko, V.M., Vlasenko, Y.G. et al. The synthesis and properties of 6-trifluoromethyl-substituted thiopyrano[3,4-d]isoxazole derivatives. Chem Heterocycl Comp 51, 630–638 (2015). https://doi.org/10.1007/s10593-015-1750-1
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DOI: https://doi.org/10.1007/s10593-015-1750-1