Photooxidative Keto-Trifluoromethylation of Styrenes by Means of an Anthraquinone-Based Organocatalyst

Published as part of the Special Topic Modern Coupling Approaches and their Strategic Applications in Synthesis

Abstract

α-Trifluoromethyl ketones are versatile building blocks for the synthesis of various trifluoromethyl-functionalized molecules. Although there are significant advantages in the development of methods toward direct transformations of styrenes into α-trifluoromethyl ketones, most procedures leading to α-trifluoromethyl ketones require heavy- or transition-metal-based complexes. Herein, a novel method is developed for the synthesis of α-trifluoromethyl ketones via anthraquinone-catalyzed photooxidative keto-trifluoromethylation of styrenes with the readily available Langlois reagent (CF₃SO₂Na) under an oxygen atmosphere. The reactions proceed smoothly to give the products in moderate to excellent yield with good selectivity.

Key words

anthraquinone - trifluoromethylation - trifluoromethyl radical - radical reaction - photoreaction

• References

• 1a Isanbor C. O’Hagan D. J. Fluorine Chem. 2006; 127: 303
• 1b Kirk KL. J. Fluorine Chem. 2006; 127: 1013
• 1c Muller K. Faeh C. Diederich F. Science 2007; 317: 1881
• 1d Hagmann WK. J. Med. Chem. 2008; 51: 4359
• 2a Fluorine in Medicinal Chemistry and Chemical Biology. Ojima I. Wiley; Chichester: 2009
• 2b Bégué J.-P. Bonnet-Delphon D. Bioorganic and Medicinal Chemistry of Fluorine . John Wiley & Sons; Hoboken: 2008

For selected recent reviews on C–CF₃ bond-forming reaction, see:
• 3a Ma J.-A. Cahard D. Chem. Rev. 2004; 104: 6119
• 3b Shimizu M. Hiyama T. Angew. Chem. Int. Ed. 2004; 44: 214
• 3c Ma J.-A. Cahard D. J. Fluorine Chem. 2007; 128: 975
• 3d Prakash GK. Hu J. Acc. Chem. Res. 2007; 40: 921
• 3e Ma J.-A. Cahard D. Chem. Rev. 2008; 108: PR1
• 3f Uneyama K. Katagiri T. Amii H. Acc. Chem. Res. 2008; 41: 817
• 3g Kumadaki I. Ando A. Sato K. Tarui A. Omote M. Synthesis 2010; 1865
• 3h Shibata N. Matsnev A. Cahard D. Beilstein J. Org. Chem. 2010; 6: 65
• 3i Dilman AD. Levin VV. Eur. J. Org. Chem. 2011; 831
• 3j Furuya T. Kamlet AS. Ritter T. Nature 2011; 473: 470
• 3k Qing F.-L. Zheng F. Synlett 2011; 1052
• 3l Roy S. Gregg BT. Gribble GW. Le V.-D. Roy S. Tetrahedron 2011; 67: 2161
• 3m Tomashenko OA. Grushin VV. Chem. Rev. 2011; 111: 4475
• 3n Macé Y. Magnier E. Eur. J. Org. Chem. 2012; 2479
• 3o Soloshonok V. Aceña J. Sorochinsky A. Synthesis 2012; 44: 1591
• 3p Studer A. Angew. Chem. Int. Ed. 2012; 51: 8950
• 3q Liu H. Gu Z. Jiang X. Adv. Synth. Catal. 2013; 355: 617
• 3r Zhang C.-P. Chen Q.-Y. Guo Y. Xiao J.-C. Gu Y.-C. Coord. Chem. Rev. 2014; 261: 28
• 4a Alvernhe G. Langlois B. Laurent A. Le Drean I. Selmi A. Weissenfels M. Tetrahedron Lett. 1991; 32: 643
• 4b Schenck HA. Lenkowski PW. Choudhury-Mukherjee I. Ko SH. Stables JP. Patel MK. Brown ML. Bioorg. Med. Chem. 2004; 12: 979
• 4c Muzalevskiy VM. Nenajdenko VG. Rulev AY. Ushakov IA. Romanenko GV. Shastin AV. Balenkova ES. Haufe G. Tetrahedron 2009; 65: 6991
• 4d Rudler H. Parlier A. Denneval C. Herson P. J. Fluorine Chem. 2010; 131: 738
• 4e Ye Y. Kunzi SA. Sanford MS. Org. Lett. 2012; 14: 4979
• 4f Li Z. Cui Z. Liu Q. Org. Lett. 2013; 15: 406

For examples of electrophilic trifluoromethylation of carbonyl compounds, see:
• 5a Umemoto T. Ishihara S. J. Am. Chem. Soc. 1993; 115: 2156
• 5b Umemoto T. Adachi K. J. Org. Chem. 1994; 59: 5692
• 5c Ma JA. Cahard D. J. Org. Chem. 2003; 68: 8726
• 5d Noritake S. Shibata N. Nomura Y. Huang Y. Matsnev A. Nakamura S. Toru T. Cahard D. Org. Biomol. Chem. 2009; 7: 3599
• 5e Allen AE. Macmillan DW. C. J. Am. Chem. Soc. 2010; 132: 4986

For examples of radical trifluoromethylation of carbonyl compounds, see:
• 6a Miura K. Taniguchi M. Nozaki K. Oshima K. Utimoto K. Tetrahedron Lett. 1990; 31: 6391
• 6b Langlois BR. Laurent E. Roidot N. Tetrahedron Lett. 1992; 33: 1291
• 6c Itoh Y. Mikami K. Org. Lett. 2005; 7: 4883
• 6d Itoh Y. Mikami K. Org. Lett. 2005; 7: 649
• 6e Itoh Y. Houk KN. Mikami K. J. Org. Chem. 2006; 71: 8918
• 6f Itoh Y. Mikami K. J. Fluorine Chem. 2006; 127: 539
• 6g Itoh Y. Mikami K. Tetrahedron 2006; 62: 7199
• 6h Mikami K. Tomita Y. Ichikawa Y. Amikura K. Itoh Y. Org. Lett. 2006; 8: 4671
• 6i Nagib DA. Scott ME. MacMillan DW. C. J. Am. Chem. Soc. 2009; 131: 10875
• 6j Pham PV. Nagib DA. MacMillan DW. C. Angew. Chem. Int. Ed. 2011; 50: 6119
• 6k Jiang H. Cheng Y. Zhang Y. Yu S. Eur. J. Org. Chem. 2013; 5485
• 6l Li L. Chen QY. Guo Y. J. Org. Chem. 2014; 79: 5145
• 6m Wang YF. Lonca GH. Chiba S. Angew. Chem. Int. Ed. 2014; 53: 1067
• 6n Su X. Huang H. Yuan Y. Li Y. Angew. Chem. Int. Ed. 2017; 56: 1338
• 6o Kawamoto T. Sasaki R. Kamimura A. Angew. Chem. Int. Ed. 2017; 56: 1342
• 7 For an example of nucleophilic trifluoromethylation of carbonyl compounds, see: Novak P. Lishchynskyi A. Grushin VV. J. Am. Chem. Soc. 2012; 134: 16167
• 8 Zhang CP. Wang ZL. Chen QY. Zhang CT. Gu YC. Xiao JC. Chem. Commun. 2011; 47: 6632
• 9 Deb A. Manna S. Modak A. Patra T. Maity S. Maiti D. Angew. Chem. Int. Ed. 2013; 52: 9747
• 10 Luo X.-Z. Luo H.-Q. Zhang Z.-P. Dong W. Synlett 2014; 25: 1307
• 11 Tomita R. Yasu Y. Koike T. Akita M. Angew. Chem. Int. Ed. 2014; 53: 7144
• 12 Li L. Chen Q.-Y. Guo Y. J. Fluorine Chem. 2014; 167: 79
• 13 Cui L. Matusaki Y. Tada N. Miura T. Uno B. Itoh A. Adv. Synth. Catal. 2013; 355: 2203
• 14 Yang Y. Liu Y. Jiang Y. Zhang Y. Vicic DA. J. Org. Chem. 2015; 80: 6639
• 15 Tada N. Ban K. Yoshida M. Hirashima S. Miura T. Itoh A. Tetrahedron Lett. 2010; 51: 6098
• 16 Maji A. Hazra A. Maiti D. Org. Lett. 2014; 16: 4524
• 17 Lu Q. Liu C. Huang Z. Ma Y. Zhang J. Lei A. Chem. Commun. 2014; 50: 14101
• 18 Yasu Y. Koike T. Akita M. Angew. Chem. Int. Ed. 2012; 51: 9567
• 19 van Ramesdonk HJ. Bakker BH. Groeneveld MM. Verhoeven JW. Allen BD. Rostron JP. J. Phys. Chem. A 2006; 110: 13145