Investigations into Transition-Metal-Catalyzed Arene Trifluoromethylation Reactions

Abstract

Trifluoromethyl-substituted arenes and heteroarenes are widely prevalent in pharmaceuticals and agrochemicals. As a result, the development of practical methods for the formation of aryl–CF₃ bonds has become an active field of research. Over the past five years, transition-metal-catalyzed cross-coupling between aryl–X (X = halide, organometallic, or H) and various ‘CF₃’ reagents has emerged as a particularly attractive approach to generating aryl–CF₃ bonds. Despite many recent advances in this area, current methods generally suffer from limitations such as poor generality, harsh reaction conditions, the requirement for stoichiometric quantities of metals, and/or the use of costly CF₃ sources. This Account describes our recent efforts to address some of these challenges by: (1) developing aryltrifluoromethylation reactions involving high oxidation state Pd intermediates, (2) exploiting AgCF₃ for C–H trifluoromethylation, and (3) achieving Cu-catalyzed trifluoromethylation with photogenerated CF₃ •.

1 Introduction

2 Part 1. Aryltrifluoromethylation via High-Valent Palladium

3 Part 2. Aryltrifluoromethylation Using AgCF₃

4 Part 3. Cu-Catalyzed Aryltrifluoromethylation with CF₃•

5 Outlook

Key words

trifluoromethylation - cross-coupling - palladium - silver - photocatalysis

• References

• 1a Schlosser M. Angew. Chem. Int. Ed. 2006; 45: 5432
• 1b Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
• 1c Hagmann WK. J. Med. Chem. 2008; 51: 4359
• 1d Kirk KL. Org. Process Res. Dev. 2008; 12: 305
• 1e Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
• 1f Tomashenko OA, Grushin VV. Chem. Rev. 2011; 111: 4475
• 1g Roy S, Gregg BT, Gribble GW, Le V.-D. Tetrahedron 2011; 67: 2161
• 2a Furuya T, Kamlet AS, Ritter T. Nature 2011; 473: 470
• 2b Grushin VV. Acc. Chem. Res. 2010; 43: 160
• 3 Swarts F. Bull. Acad. R. Belg. 1892; 24: 309
• 4a Grushin VV, Marshall WJ. J. Am. Chem. Soc. 2006; 128: 12644
• 4b Bakhmutov VI, Bozoglian F, Gomez K, Gonzalez G, Grushin VV, Macgregor SA, Martin E, Miloserdov FM, Novikov MA, Panetier JA, Romashov LV. Organometallics 2012; 31: 1315
• 5a Dubinina GG, Furutachi H, Vicic DA. J. Am. Chem. Soc. 2008; 130: 8600
• 5b Dubinina GG, Ogikubo J, Vicic DA. Organometallics 2008; 27: 6233
• 6 Oishi M, Kondo H, Amii H. Chem. Commun. 2009; 1909
• 7 Cho EJ, Senecal TD, Kinzel T, Zhang Y, Watson DA, Buchwald SL. Science 2010; 328: 1679
• 8a Hickman AJ, Sanford MS. Nature 2012; 484: 177
• 8b Muniz K. Angew. Chem. Int. Ed. 2009; 48: 9412
• 8c Lyons T, Sanford MS. Chem. Rev. 2010; 110: 1147
• 9a Ball ND, Kampf JW, Sanford MS. J. Am. Chem. Soc. 2010; 132: 2878
• 9b Ball ND, Gary JB, Ye Y, Sanford MS. J. Am. Chem. Soc. 2011; 133: 7577
• 10a Ball ND, Sanford MS. J. Am. Chem. Soc. 2009; 131: 3796
• 10b Ball ND, Kampf JW, Sanford MS. Dalton Trans. 2010; 632
• 10c Canty AJ. Acc. Chem. Res. 1992; 25: 83
• 11a Racowski JM, Gary JB, Sanford MS. Angew. Chem. Int. Ed. 2012; 51: 3414
• 11b Furuya T, Benitez D, Tkatchouk E, Strom AE, Tang P, Goddard WA. I, Ritter T. J. Am. Chem. Soc. 2010; 132: 3793
• 12 Markies BA, Canty AJ, Boersma J, van Koten G. Organometallics 1994; 13: 2053
• 13 Mu X, Chen S, Zhen X, Liu G. Chem. Eur. J. 2011; 17: 6039
• 14 Mu X, Wu T, Wang H.-Y, Guo Y.-L, Liu G. J. Am. Chem. Soc. 2012; 134: 878
• 15 Racowski JM, Dick AR, Sanford MS. J. Am. Chem. Soc. 2009; 131: 10974
• 16a Powers DC, Ritter T. Acc. Chem. Res. 2012; 45: 840
• 16b Canty AJ. Dalton Trans. 2009; 10409
• 17 Ye Y, Ball ND, Kampf JW, Sanford MS. J. Am. Chem. Soc. 2010; 132: 14682
• 18 Wang X, Truesdale L, Yu J.-Q. J. Am. Chem. Soc. 2010; 132: 3648
• 19a Furuya T, Strom AE, Ritter T. J. Am. Chem. Soc. 2009; 131: 1662
• 19b Furuya T, Ritter T. Org. Lett. 2009; 11: 2860
• 19c Tang P, Ritter T. Tetrahedron 2011; 67: 4449
• 20a Tyrra WE, Naumann D. J. Fluorine Chem. 2004; 125: 823
• 20b Weng Z, Lee R, Jia W, Yuan Y, Wang W, Feng X, Huang KW. Organometallics 2011; 30: 3229
• 21 Ye Y, Lee SH, Sanford MS. Org. Lett. 2011; 13: 5464
• 22a Wakselman C, Tordeux M. J. Chem. Soc., Chem. Commun. 1987; 1701
• 22b Akiyama T, Kato K, Kajitani M, Sakaguchi Y, Nakamura J, Hayashi H, Sugimori A. Bull. Chem. Soc. Jpn. 1988; 61: 3531
• 22c Sawada H, Nakayama M. J. Fluorine Chem. 1990; 46: 423
• 22d Langlois BR, Laurent E, Roidot M. Tetrahedron Lett. 1991; 32: 7525
• 22e McClinton MA, McClington DA. Tetrahedron 1992; 48: 6555
• 22f Kamigata N, Ohtsuka T, Fukushima T, Yoshida M, Shimizu T. J. Chem. Soc., Perkin Trans. 1 1994; 1339
• 22g Kino T, Nagase Y, Ohtsuka Y, Yamamoto K, Uraguchi D, Tokuhisa K, Yamakawa T. J. Fluorine Chem. 2010; 131: 98
• 22h Loy RN, Sanford MS. Org. Lett. 2011; 13: 2548
• 23 Ji Y, Brueckl T, Baxter RD, Fujiwara Y, Seiple IB, Su S, Blackmond DG, Baran PS. Proc. Natl. Acad. Sci. U.S.A. 2011; 108: 14411
• 24 Nagib DA, MacMillan DW. C. Nature 2011; 480: 224
• 25 Iqbal N, Choi S, Ko E, Cho EJ. Tetrahedron Lett. 2012; 53: 2005
• 26a Chu L, Qing FL. Org. Lett. 2010; 12: 5060
• 26b Senecal TD, Parsons AT, Buchwald SL. J. Org. Chem. 2011; 76: 1174
• 26c Khan BA, Buba AE, Gooßen LJ. Chem. Eur. J. 2012; 18: 1577
• 26d Jiang X, Chu L, Qing F.-L. J. Org. Chem. 2012; 77: 1251
• 27 For an example of trifluoromethyl copper(I) reagent derived from CF₃ ^–, see: Morimoto H, Tsubogo T, Litvinas ND, Hartwig JF. Angew. Chem. Int. Ed. 2011; 50: 3793
• 28a Liu T, Shen Q. Org. Lett. 2011; 13: 2342
• 28b Xu J, Luo DF, Xiao B, Liu J, Gong TJ, Fu Y, Liu L. Chem. Commun. 2011; 47: 4300
• 28c Zhang CP, Wang ZL, Chen QY, Zhang CT, Gu YC, Xiao JC. Angew. Chem. Int. Ed. 2011; 50: 1896
• 29a Nagib DA, Scott ME, MacMillan DW. C. J. Am. Chem. Soc. 2009; 131: 10875
• 29b Pham PV, Nagib DA, MacMillan DW. C. Angew. Chem. Int. Ed. 2011; 50: 6119
• 30 Ye Y, Sanford MS. J. Am. Chem. Soc. 2012; 134: 9034
• 31 Li YC. T, Wang H, Zhang R, Jin K, Wang X, Duan C. Synlett 2011; 1713
• 32 Zhang C.-P, Cai J, Zhou C.-B, Wang X.-P, Zheng X, Gu Y.-C, Xiao J.-C. Chem. Commun. 2011; 47: 9516
• 33 Besset T, Schneider C, Cahard D. Angew. Chem. Int. Ed. 2012; 51: 5048