钯催化的芳基C-H键三氟甲硫基化反应
收稿日期: 2015-03-27
网络出版日期: 2015-05-15
基金资助
项目受科技部(No.973-2015CB856600)、国家自然科学基金(Nos.21225210,21421091,21472219)和上海市科学技术委员会(No.12ZR1453400)资助.
Palladium-Catalyzed Trifluoromethylthiolation of Arenes via C-H Activation
Received date: 2015-03-27
Online published: 2015-05-15
Supported by
Project supported by the National Basic Research Program of China(No. 973-2015CB856600), the National Natural Science Foundation of China(Nos. 21225210, 21421091, 21472219) and Science Technology Commission of the Shanghai Municipality(No. 12ZR1453400).
徐佳斌 , 陈品红 , 叶金星 , 刘国生 . 钯催化的芳基C-H键三氟甲硫基化反应[J]. 化学学报, 2015 , 73(12) : 1294 -1297 . DOI: 10.6023/A15030211
Fluorinated organic compounds are widely used as pharmaceuticals, agrochemicals and materials. Among them, the trifluoromethylthio(-SCF3) compounds has attracted much attention owning to its strong electron-withdrawing nature and high lipophilicity. Therefore, the development of new trifluoromethylthiolation methods has attracted great interest in synthetic organic chemistry. Traditional approaches for the synthesis of trifluoromethylthiolated arenes include halogen-fluorine exchange and the trifluoromethylation of sulfur-containing compounds such as disulfides, thiols, which suffer from poor functional compatibility and yield. Recent progress on the transition metal-catalyzed directing trifluoromethylthiolation using SCF3 reagents provided an efficient approach to the target. Herein, we reported a Pd(II)-catalyzed highly selective C-H trifluoromethylthiolation of arenes. Different type of pyridines could be used as efficient directing groups for this reaction. In this reaction, benzoyl chloride was found to be crucial to activate the trifluoromethanesulfanamide 2a. It provides an efficient way for the synthesis of ortho-SCF3 substituted arenes in high yields. A representative procedure for this reaction is as following:To a 10 mL glass tube, Pd(OAc)2(4.4 mg, 0.02 mmol), AgOAc(33 mg, 0.2 mmol), PhNHSCF3(50μL, 0.5 mmol), substrate(0.2 mmol) and PhCOCl(58μL, 0.5 mmol) were dissolved in dry DMF(1 mL) under N2 atmosphere. The tube was sealed and the mixture was stirred at 120℃ for 12 h, and then cooled to room temperature. The mixture was concentrated and purified by column chromatography on silica gel with a gradient eluent of petroleum ether and ethyl acetate(range from 15:1 to 4:1) to provide the products in 62%~91% yields.
[1] (a) Hollingworth, C.; Gouverneur, V. Chem. Commun. 2012, 48, 2929.
(b) Coenen, H. H.; Ermert, J. Curr. Radiopharm. 2010, 3, 163.
(c) Zhang, X. J.; Lai, T. B.; Kong, R. Y. C. Top. Curr. Chem. 2012, 308, 365.
(d) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320.
(e) Jeschke, P. ChemBioChem 2004, 5, 570.
(f) Zhu, H.; Liu, G. Acta Chim. Sinica 2012, 70, 2404.(朱海涛, 刘国生, 化学学报, 2012, 70, 2404.)
(g) Lv, H.; Zhang, C.; Huang, J.; Zhao, Q.; Ma, Z.; Xiao, J. Acta Chim. Sinica 2012, 70, 1125.(吕会朝, 张成潘, 黄晋, 赵巧玲, 马志, 肖吉昌, 化学学报, 2012, 70, 1125.)
(h) Pan, F.; Shi, Z. Acta Chim. Sinica 2012, 70, 1679.(潘菲, 施章杰, 化学学报, 2012, 70, 1679.)
(i) Ni, C.; Zhu, L.; Hu, J. Acta Chim. Sinica 2015, 73, 90.(倪传法, 朱林桂, 胡金波, 化学学报, 2015, 73, 90.).
[2] (a) Leo, A.; Hansch, C.; Elkins, D. Chem. Rev. 1971, 71, 525.
(b) Hansch, C.; Leo, A.; Unger, S. H.; Kim, K. H.; Nikaitani, D.; Lien, E. J. J. Med. Chem. 1973, 16, 1207.
(c) Leroux, F.; Jeschke, P.; Schlosser, M. Chem. Rev. 2005, 105, 827.
[3] (a) Boiko, V. N. Beilstein J. Org. Chem. 2010, 6, 880.
(b) Tlili, A.; Billard, T. Angew. Chem., Int. Ed. 2013, 52, 6818.
(c) Liang, T.; Neumann, C. N.; Ritter, T. Angew. Chem., Int. Ed. 2013, 52, 8214.
(d) Toulgoat, F.; Alazet, S.; Billard, T. Eur. J. Org. Chem. 2014, 2415.
[4] (a) Yarovenko, N. N.; Vasileva, A. S.; Gen, J. Chem. USSR(Engl. Transl.) 1958, 28, 2537;
(b) Nodiff, E.; Lipschutz, A. S.; Craig, P. N.; Gordon, M. J. Org. Chem. 1960, 25, 60;
(c) Feiring, A. E. J. Org. Chem. 1979, 44, 2907.
[5] For selected examples, see:(a) Billard, T.; Blond, G.; Langlois, B. R. Tetrahedron Lett. 1997, 38, 65;
(b) Billard, T.; Blond, G.; Langlois, B. R. Tetrahedron Lett. 2001, 42, 2473;
(c) Kieltsch, I.; Eisenberger, P.; Togni, A. Angew. Chem., Int. Ed. 2007, 46, 754.
[6] For reviews, see:(a) Chen, P.; Liu, G. Synthesis 2013, 45, 2919.
(b) Yang, X.; Wu, T.; Phipps, R. J.; Toste, F. D. Chem. Rev. 2015, 115, 826.
(c) He, W.-M.; Weng, Z.-Q. Prog. Chem. 2013, 25, 1071.(何伟明, 翁志强, 化学进展, 2013, 25, 1071.)
(d) Zhang, K.; Xu, X.; Qing, F. Chin. J. Org. Chem. 2015, 35, 556.(张柯, 徐修华, 卿凤翎, 有机化学, 2015, 35, 556.)
[7] For selected metal-mediated trifluoromethylthiolation reactions, see:(a) Chen, Q.-Y.; Duan, J.-X. J. Chem. Soc., Chem. Commun. 1993, 918;
(b) Zhang, C.-P.; Vicic, D. A. Chem. Asian J. 2012, 7, 1756;
(c) Chen, C.; Chu, L.-L.; Qing, F.-L. J. Am. Chem. Soc. 2012, 134, 12454;
(d) Weng, Z.; He, W.; Chen, C.; Lee, R.; Dan, D.; Lai, Z.; Kong, D.; Yuan, Y.; Huang, K.-W. Angew. Chem., Int. Ed. 2013, 52, 1548.
[8] Teverovskiy, G.; Surry, D. S.; Buchwald, S. L. Angew. Chem., Int. Ed. 2011, 50, 7312.
[9] Zhang, C. P.; Vicic, D. A. J. Am. Chem. Soc. 2012, 134, 183.
[10] Yin, G.; Kalvet, I.; Englert, U.; Schoenebeck, F. J. Am. Chem. Soc. 2015, 137, 4164.
[11] Shao, X.; Wang, X.-Q.; Yang, T.; Lu, L.; Shen, Q. Angew. Chem., Int. Ed. 2013, 52, 3457.
[12] Pluta, R.; Nikolaienko, P.; Rueping, M. Angew. Chem., Int. Ed. 2014, 53, 1650.
[13] Mu, X.; Zhang, H.; Chen, P.; Liu, G. Chem. Sci. 2014, 5, 275.
[14] Xu, J.; Mu, X.; Chen, P.; Ye, J.; Liu, G. Org. Lett. 2014, 16, 3942.
[15] Chen, C.; Xie, Y.; Chu, L.; Wang, R.-W.; Zhang, X.; Qing, F. L. Angew. Chem., Int. Ed. 2012, 51, 2492.
[16] Tran, L. D.; Popov, I.; Daugulis, O. J. Am. Chem. Soc. 2012, 134, 18237.
[17] Xu, C.; Shen, Q. Org. Lett. 2014, 16, 2046.
[18] Yin, W.; Wang, Z.; Huang, Y. Adv. Synth. Catal. 2014, 356, 2998.
[19] (a) Ferry, A. l.; Billard, T.; Langlois, B. R.; Bacqué, E. J. Org. Chem. 2008, 73, 9362;
(b) Ferry, A.; Billard, T.; Langlois, B. R.; Bacqué, E. Angew. Chem., Int. Ed. 2009, 48, 8551;
(c) Ferry, A.; Billard, T.; Bacqué, E.; Langlois, B. R. J. Fluorine Chem. 2012, 134, 160;
(d) Baert, F.; Colomb, J.; Billard, T. Angew. Chem., Int. Ed. 2012, 51, 10382;
(e) Lu, J.; Chu, L.; Qing, F.-L. Org. Lett. 2013, 15, 894.
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