Conversion of Aromatic Amino into Trifluoromethyl Groups through a Sandmeyer­-Type Transformation

Abstract

A novel strategy for aromatic trifluoromethylation by converting amino into trifluoromethyl groups via a Sandmeyer-type reaction is reported. The transformation involves diazotization of the aromatic amines with tert-butyl nitrite and hydrochloric acid to form aryldiazonium chlorides, followed by trifluoromethylation with trifluoromethylsilver at low temperature. Various readily available aromatic amines are smoothly converted under mild conditions.

Key words

trifluoromethylation - aromatic amines - diazonium salts - silver - Sandmeyer reaction

• References

• 1a Kirsch P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications. Wiley-VCH; Weinheim: 2004
• 1b Müller K, Faeh C, Diederich F. Science 2007; 317: 1881

For reviews, see:
• 2a Prakash GK. S, Yudin AK. Chem. Rev. 1997; 97: 757
• 2b Shimizu M, Hiyama T. Angew. Chem. Int. Ed. 2005; 44: 214
• 2c Schlosser M. Angew. Chem. Int. Ed. 2006; 45: 5432
• 2d Ma J.-A, Cahard D. J. Fluorine Chem. 2007; 128: 975
• 2e Ma J.-A, Cahard D. Chem. Rev. 2008; 108: PR1
• 2f Tomashenko OA, Grushin VV. Chem. Rev. 2011; 111: 4475
• 2g Besset T, Schneider C, Cahard D. Angew. Chem. Int. Ed. 2012; 51: 5048
• 2h Macé Y, Magnier E. Eur. J. Org. Chem. 2012; 2479
• 2i Shibata N, Matsnev A, Cahard D. Beilstein J. Org. Chem. 2010; 6: 65
• 2j Wu XF, Neumann H, Beller M. Chem. Asian J. 2012; 7: 1744
• 2k Studer A. Angew. Chem. Int. Ed. 2012; 51: 8950
• 2l Liang T, Neumann CN, Ritter T. Angew. Chem. Int. Ed. 2013; 52: 8214
• 3 Swarts F. Bull. Soc. Chim. Belg. 1892; 24: 309
• 4a McLoughlin VC. R, Thrower J. Tetrahedron 1969; 25: 5921
• 4b Chen Q.-Y, Wu S.-W. J. Chem. Soc., Chem. Commun. 1989; 705
• 4c Chen Q.-Y, Duan J.-X. J. Chem. Soc., Chem. Commun. 1993; 1389
• 4d Oishi M, Kondo H, Amii H. Chem. Commun. 2009; 1909
• 4e Cho EJ, Senecal TD, Kinzel T, Zhang Y, Watson DA, Buchwald SL. Science 2010; 328: 1679
• 5a Chu L, Qing F.-L. Org. Lett. 2010; 12: 5060
• 5b Senecal TD, Parsons AT, Buchwald SL. J. Org. Chem. 2011; 76: 1174
• 5c Liu T, Shen Q. Org. Lett. 2011; 13: 2342
• 5d Xu J, Luo D.-F, Xiao B, Liu Z.-J, Gong T.-J, Fu Y, Liu L. Chem. Commun. 2011; 47: 4300
• 5e Zhang C.-P, Cai J, Zhou C.-B, Wang X.-P, Zheng X, Gu Y.-C, Xiao J.-C. Chem. Commun. 2011; 47: 9516
• 5f Litvinas ND, Fier PS, Hartwig JF. Angew. Chem. Int. Ed. 2012; 51: 536
• 5g Novák P, Lishchynskyi A, Grushin VV. Angew. Chem. Int. Ed. 2012; 51: 7767
• 5h Ye Y, Sanford MS. J. Am. Chem. Soc. 2012; 134: 9034

For recent reports, see:
• 6a Nagib DA, MacMillan DW. C. Nature 2011; 480: 224
• 6b 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
• 6c Ye Y, Lee SH, Sanford MS. Org. Lett. 2011; 13: 5464
• 6d Fujiwara Y, Dixon JA, O’Hara F, Funder ED, Dixon DD, Rodriguez RA, Baxter RD, Herlé B, Sach N, Collins MR, Ishihara Y, Baran PS. Nature 2012; 492: 95
• 6e Studer A. Angew. Chem. Int. Ed. 2012; 51: 8950

For trifluoromethylation via transition-metal-catalyzed C–H bond activation, see:
• 7a Wang X, Truesdale L, Yu J.-Q. J. Am. Chem. Soc. 2010; 132: 3648
• 7b Zhang X.-G, Dai H.-X, Wasa M, Yu J.-Q. J. Am. Chem. Soc. 2012; 134: 11948
• 7c Hafner A, Bräse S. Angew. Chem. Int. Ed. 2012; 51: 3713
• 7d Zhang L.-S, Chen K, Chen G.-H, Li B.-J, Luo S, Guo Q.-Y, Wei J.-B, Shi Z.-J. Org. Lett. 2013; 15: 10

For recent reviews on arenediazonium salts, see:
• 8a Mo F, Dong G, Zhang Y, Wang J. Org. Biomol. Chem. 2013; 11: 1582
• 8b Hari DP, König B. Angew. Chem. Int. Ed. 2013; 52: 4734
• 9a Sandmeyer T. Ber. Dtsch. Chem. Ges. 1884; 17: 1633
• 9b Sandmeyer T. Ber. Dtsch. Chem. Ges. 1884; 17: 2650
• 9c Balz G, Schiemann G. Ber. Dtsch. Chem. Ges. 1927; 60: 1186
• 10a Furuya T, Strom AE, Ritter T. J. Am. Chem. Soc. 2009; 131: 1662
• 10b Tang P, Furuya T, Ritter T. J. Am. Chem. Soc. 2010; 132: 12150
• 10c Huang C, Liang T, Harada S, Lee E, Ritter T. J. Am. Chem. Soc. 2011; 133: 13308
• 11 Tyrra WE. J. Fluorine Chem. 2001; 112: 149
• 12a Naumann D, Wessel W, Hahn J, Tyrra W. J. Organomet. Chem. 1997; 547: 79
• 12b Eujen R, Hoge B, Brauer DJ. Inorg. Chem. 1997; 36: 1464
• 12c Weng Z, Lee R, Jia W, Yuan Y, Wang W, Feng X, Huang K.-W. Organometallics 2011; 30: 3229
• 13 Kremlev MM, Mushta AI, Tyrra W, Naumann D, Fischer HT. M, Yagupolskii YL. J. Fluorine Chem. 2007; 128: 1385
• 14a Ruppert I, Schlich K, Volbach W. Tetrahedron Lett. 1984; 25: 2195
• 14b Prakash GK. S, Krishnamurti R, Olah GA. J. Am. Chem. Soc. 1989; 111: 393
• 14c Prakash GK. S, Jog PV, Batamack PT. D, Olah GA. Science 2012; 338: 1324
• 15a Doyle MP, Siegfried B, Dellaria JF. Jr. J. Org. Chem. 1977; 42: 2426
• 15b Doyle MP, Dellaria JF. Jr, Siegfried B, Bishop SW. J. Org. Chem. 1977; 42: 3494
• 16a Wang X, Xu Y, Mo F, Ji G, Qiu D, Feng J, Ye Y, Zhang S, Zhang Y, Wang J. J. Am. Chem. Soc. 2013; 135: 10330
• 16b Dai J.-J, Fang C, Xiao B, Yi J, Xu J, Liu Z.-J, Lu X, Liu L, Fu Y. J. Am. Chem. Soc. 2013; 135: 8436
• 16c Danoun G, Bayarmagnai B, Grünberg MF, Gooßen LJ. Angew. Chem. Int. Ed. 2013; 52: 7972
• 16d Browne DL. Angew. Chem. Int. Ed. 2014; 53: 1482
• 17a Mo F, Jiang Y, Qiu D, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2010; 49: 1846
• 17b Qiu D, Jin L, Zheng Z, Meng H, Mo F, Wang X, Zhang Y, Wang J. J. Org. Chem. 2013; 78: 1923