A Broadly Applicable Copper Reagent for Trifluoromethylations and Perfluoroalkylations of Aryl Iodides and Bromides
2011; Wiley; Volume: 50; Issue: 16 Linguagem: Inglês
10.1002/anie.201100633
ISSN1521-3773
AutoresHiroyuki Morimoto, Tetsu Tsubogo, Nichole D. Litvinas, John F. Hartwig,
Tópico(s)Catalytic Cross-Coupling Reactions
ResumoAngewandte Chemie International EditionVolume 50, Issue 16 p. 3793-3798 Communication A Broadly Applicable Copper Reagent for Trifluoromethylations and Perfluoroalkylations of Aryl Iodides and Bromides† Dr. Hiroyuki Morimoto, Dr. Hiroyuki Morimoto Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801 (USA), Fax: (+1) 217-244-9248Search for more papers by this authorTetsu Tsubogo, Tetsu Tsubogo Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801 (USA), Fax: (+1) 217-244-9248Search for more papers by this authorDr. Nichole D. Litvinas, Dr. Nichole D. Litvinas Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801 (USA), Fax: (+1) 217-244-9248Search for more papers by this authorProf. Dr. John F. Hartwig, Corresponding Author Prof. Dr. John F. Hartwig [email protected] Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801 (USA), Fax: (+1) 217-244-9248Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801 (USA), Fax: (+1) 217-244-9248Search for more papers by this author Dr. Hiroyuki Morimoto, Dr. Hiroyuki Morimoto Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801 (USA), Fax: (+1) 217-244-9248Search for more papers by this authorTetsu Tsubogo, Tetsu Tsubogo Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801 (USA), Fax: (+1) 217-244-9248Search for more papers by this authorDr. Nichole D. Litvinas, Dr. Nichole D. Litvinas Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801 (USA), Fax: (+1) 217-244-9248Search for more papers by this authorProf. Dr. John F. Hartwig, Corresponding Author Prof. Dr. John F. Hartwig [email protected] Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801 (USA), Fax: (+1) 217-244-9248Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801 (USA), Fax: (+1) 217-244-9248Search for more papers by this author First published: 25 March 2011 https://doi.org/10.1002/anie.201100633Citations: 412 † The authors thank the NIH (GM-58108 to J.F.H. and 1F32M093540-01 to N.D.L.) and JSPS for a postdoctoral fellowship to H.M. We thank Dr. Ramesh Giri for reagents, and Dr. Vera V. Mainz for helpful discussion concerning NMR experiments. T.T. was supported in part by Global COE Program (Chemistry Innovation through Cooperation of Science and Engineering), MEXT (Japan). Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract Well compatible: The trifluoromethylations and perfluoroalkylations of aryl iodides and some aryl bromides with trifluoromethyl and perfluoroalkylcopper(I) phenanthroline complexes occur with broad scope at 25–50 °C (see scheme). The trifluoromethyl complex is prepared from inexpensive reagents and can be used in situ or isolated. The reactions tolerate a range of substituents and also occur with heteroaromatic systems. References 1S. Purser, P. R. Moore, S. Swallow, V. Gouverneur, Chem. Soc. Rev. 2008, 37, 320– 330. 2For approaches to trifluoromethylation of aryl halides, see the following and reference [3]: 2aE. J. Cho, T. D. Senecal, T. Kinzel, Y. Zhang, D. A. Watson, S. L. Buchwald, Science 2010, 328, 1679– 1681; 2bV. V. Grushin, W. J. Marshall, J. Am. Chem. Soc. 2006, 128, 12644– 12645; 2cT. Kitazume, N. Ishikawa, Chem. Lett. 1982, 137– 140; 2dF. Monnier, M. Taillefer, Angew. Chem. 2009, 121, 7088– 7105; Angew. Chem. Int. Ed. 2009, 48, 6954– 6971; 2eD. M. Wiemers, D. J. Burton, J. Am. Chem. Soc. 1986, 108, 832– 834; 2fF. Cottet, M. Schlosser, Eur. J. Org. Chem. 2002, 327– 330; 2gA. Kütt, V. Movchun, T. Rodima, T. Dansauer, E. B. Rusanov, I. Leito, I. Kaljurand, J. Koppel, V. Pihl, I. Koppel, G. Ovsjannikov, L. Toom, M. Mishima, M. Medebielle, E. Lork, G.-V. Roschenthaler, I. A. Koppel, A. A. 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Chem. 1991, 56, 984– 989. 14Yields were obtained by the reaction of 10 % CuI, 10 % 1,10-phenanthroline, 2 equiv KF, 2 equiv TESCF3 in a 1:1 mixture of NMP:DMF at 60 °C for 24 h, as described by Amii et al.[3] Yields were determined by 19F NMR spectroscopy with 4-CF3OC6H4OMe as internal standard. Substrate 3 b gave 4 b in 36 % yield. Substrate 3 c gave 4 c in 43 % yield. Substrate 3 g gave 4 g in approximately 10 % yield with the trifluoromethyl carbinols as the major products. Substrate 3 e gave none of 4 e and formed exclusively the trifluoromethyl carbinol product. 3 p gave 4 p in 41 % yield; 3 o gave 4 o in 43 % yield. Substrates 3 l and 3 m gave 4 l and 4 m in 17 and 39 % yield. 15W. W. Lin, O. Baron, P. Knochel, Org. Lett. 2006, 8, 5673– 5676. 16S. Kobayashi, H. Ishitani, Patent US 6476250 B1, 2002. 17T. R. Wu, L. X. Shen, J. M. Chong, Org. Lett. 2004, 6, 2701– 2704. 18Q. Y. Chen, S. W. Wu, J. Chem. Soc. Chem. Commun. 1989, 705– 706. 19G. E. Carr, R. D. Chambers, T. F. Holmes, D. 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