Synthesis, Table of Contents Synthesis 2012; 44(6): 966-972DOI: 10.1055/s-0031-1290246 paper © Georg Thieme Verlag Stuttgart · New York Copper-Catalyzed Thiolation Cyclization of 1-Chloro-1,5-enynes with Sodium Hydrosulfide: Synthesis of CF3-Containing 1H-Isothiochromenes Shuai Shi College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, P. R. of China, Fax: +86(577)86689615 Email: zxg@wzu.edu.cn , Lei-Lei Sun College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, P. R. of China, Fax: +86(577)86689615 Email: zxg@wzu.edu.cn , Zhi-Yong Liao College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, P. R. of China, Fax: +86(577)86689615 Email: zxg@wzu.edu.cn , Xing-Guo Zhang* College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, P. R. of China, Fax: +86(577)86689615 Email: zxg@wzu.edu.cn › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract A copper-catalyzed regio- and stereoselective 6-exo-dig cyclization of 1-chloro-1,5-enynes with sodium hydrosulfide has been developed. In the presence of copper(I) iodide and sodium tert-butoxide, a variety of (Z)-1-methylene-3-(trifluoromethyl)-1H-isothiochromenes were prepared in moderate to good yields via thiolation cyclization of 1-alkynyl-2-(2-chloro-3,3,3-trifluoroprop-1-enyl)benzenes with sodium hydrosulfide. Key words Key wordscopper - thiolation - 6-exo-dig cyclization - 1H-isothiochromenes - sodium hydrosulfide Full Text References References 1a Crenshaw RR, Jeffries AT, Luke GM, Cheney C, Bialy G. J. Med. Chem. 1971; 14: 1185 1b Natsugari H, Tawadа H, Ikeda H. EP 481,383, 1992 ; Chem. Abstr. 1992, 117, 48326 1c Attardo G, Kraus JL, Courchesne M, Lamonthe S, Lavallee JF, Lebeau E, Nguyen D, Rej R, St-Denis Y, Wang W, Xu Y.-C, Barbeau F, Belleau B. US 5,593,970 1997 ; Chem. Abstr. 1997, 126, 199791 1d Bertenshaw SR, Talley JJ, Rogier DJ, Graneto MJ, Koboldt CM, Zhang Y. Bioorg. Med. Chem. Lett. 1996; 6: 2827 1e Toshima K, Ohta K, Ohtsuka A, Matsumura S, Nakata M. J. Chem. Soc., Chem. Commun. 1993; 1406 2a Pokhodylol NT, Matiychukl VS, Obushak MD. Chem. Heterocycl. Compd. (Engl. Transl.) 2010; 46: 140 2b Klein TR, Bergemann M, Yehia NA. M, Fanghänel E. J. Org. Chem. 1998; 63: 4626 3a Schlosser M. Angew. Chem. Int. Ed. 2005; 44: 214 3b Muller K, Faeh C, Diederich F. Science 2007; 317: 1881 3c Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320 3d Hagmann WK. J. Med. Chem. 2008; 51: 4359 3e Welch JT. Tetrahedron 1987; 43: 3123 4 Legrand L, Lozac’h N. Bull. Soc. Chim. Fr. 1970; 2244 5 Kobayashi G, Matsuda Y, Natsuki R, Yamaguchi H, Tominaga Y. Yakugaku Zasshi 1972; 92: 449 6 Schneider CC, Bortolatto C, Back DF, Menezes PH, Zeni G. Synthesis 2011; 413 7a Beletskaya IP, Ananikov VP. Chem. Rev. 2011; 111: 1596 7b Ley SV, Thomas AW. Angew. Chem. Int. Ed. 2003; 42: 5400 7c Kondo T, Mitsudo T. Chem. Rev. 2000; 100: 3205 7d Ma D, Cai Q. Acc. Chem. Res. 2008; 41: 1450 7e Jiang Y, Qin Y, Xie S, Zhang X, Dong J, Ma D. Org. Lett. 2009; 11: 5250 7f Xu H.-J, Liang Y.-F, Cai Z.-Y, Qi H.-X, Yang C.-Y, Feng Y.-S. J. Org. Chem. 2011; 76: 2296 8a Samanta R, Antonchick AP. Angew. Chem. Int. Ed. 2011; 50: 5217 8b Zeng F, Alper H. Org. Lett. 2011; 13: 2868 8c Qin X, Cong X, Zhao D, You J, Lan J. Chem. Commun. 2011; 47: 5611 8d Guilarte V, Fernández-Rodríguez MA, García-García P, Hernando E, Sanz R. Org. Lett. 2011; 13: 5100 8e Nakamura I, Sato T, Terada M, Yamamoto Y. Org. Lett. 2007; 9: 4081 8f Shi L, Liu X, Zhang H, Jiang Y, Ma D. J. Org. Chem. 2011; 76: 4200 8g Kunz K, Scholz U, Ganzer D. Synlett 2003; 2428 9 Sun L.-L, Deng C.-L, Tang R.-Y, Zhang X.-G. J. Org. Chem. 2011; 76: 7546 10a Ma D, Xie S, Xue P, Zhang X, Dong J, Jiang Y. Angew. Chem. Int. Ed. 2010; 48: 4222 10b Zhu J.-T, Chen Z.-X, Xie H.-B, Li S, Wu Y.-M. Org. Lett. 2010; 12: 2434 10c You W, Yan X.-Y, Liao Q, Xi C.-J. Org. Lett. 2010; 12: 3930 10d Kashiki T, Shinamura S, Kohara M, Miyazaki E, Takimiya K, Ikeda M, Kuwabara H. Org. Lett. 2009; 11: 2473 10e Saito M, Yamamoto T, Osaka I, Miyazaki E, Takimiya K, Kuwabara H, Ikeda M. Tetrahedron Lett. 2010; 51: 5277 This compound was prepared from the Sonogashira reaction of 2-bromobenzaldehyde and phenylacetylene, and then reacted with CF3CCl3, see: 11a Gao K, Wu J. Org. Lett. 2008; 10: 2251 11b Fujita M, Hiyama T. Bull. Chem. Soc. Jpn. 1987; 60: 4377 12 Li C.-L, Zhang X.-G, Tang R.-Y, Zhong P, Li J.-H. J. Org. Chem. 2010; 75: 7037 Supplementary Material Supplementary Material Supporting Information
