Synthesis 2016; 48(15): 2376-2384
DOI: 10.1055/s-0035-1561433
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© Georg Thieme Verlag Stuttgart · New York

Detrifluoroacetylative Generation of Halogenated Enolates: Practical Access to Perhalogenated Ketones and Alkenes

Kaluvu Balaraman
Georgetown University, Chemistry Department, Washington, DC, USA   Email: cw27@georgetown.edu
,
Max Moskowitz
Georgetown University, Chemistry Department, Washington, DC, USA   Email: cw27@georgetown.edu
,
Yang Liu
Georgetown University, Chemistry Department, Washington, DC, USA   Email: cw27@georgetown.edu
,
Christian Wolf*
Georgetown University, Chemistry Department, Washington, DC, USA   Email: cw27@georgetown.edu
› Author Affiliations
Further Information

Publication History

Received: 29.02 2016

Accepted after revision: 11 March 2016

Publication Date:
20 April 2016 (online)


Abstract

Sequential chlorination/fluorination of aromatic trifluoroacetylated ketones gives 1-aryl 2-chloro-2,4,4,4-tetrafluorobutan-1,3-dione hydrates that are used for the synthesis of ketones and alkenes exhibiting a terminal bromochlorofluoromethyl group. The hydrates undergo detrifluoroacetylative cleavage and subsequent bromination in the presence of a copper(II) bisoxazoline catalyst, K2CO3, and NBS at room temperature. The corresponding bromochlorofluoromethyl ketones can be applied in Wittig and Horner–Wadsworth–Emmons reactions and dibromoalkenylations.

Supporting Information

 
  • References

    • 1a Smith BR, Eastman CM, Njardarson JT. J. Med. Chem. 2014; 57: 9764
    • 1b Wang J, Sanchez-Rosello M, Acena JL, del Pozo C, Sorochinsky AE, Fustero S, Soloshonok VA, Liu H. Chem. Rev. 2014; 114: 2432
  • 2 Zhou Y, Wang J, Gu Z, Wang S, Zhu W, Acena JL, Soloshonok VA, Izawa K, Liu H. Chem. Rev. 2016; 116: 422
    • 3a Hargreaves MK, Barrett GC, Hall DM, Modarai B. J. Chem. Soc. C 1971; 279
    • 3b Hargreaves MK, Modarai B. J. Chem. Soc. C 1971; 1013
    • 3c Doyle TR, Vogl O. J. Am. Chem. Soc. 1989; 111: 8510
    • 3d Doyle TR, Vogl O. Monatsh. Chem. 1990; 121: 31
    • 4a Yang Z.-Y. J. Org. Chem. 2003; 68: 4410
    • 4b Zhao Y, Gao B, Hu J. J. Am. Chem. Soc. 2012; 134: 5790
    • 5a Kvicala J, Stambasky J, Skalicky M, Paleta O. J. Fluorine Chem. 2005; 126: 1390
    • 5b Petko KI, Kot SY, Yagupolskii LM. J. Fluorine Chem. 2008; 129: 1119
    • 5c Matsnev AV, Qing S.-Y, Stanton MA, Berger KA, Haufe G, Thrasher JS. Org. Lett. 2014; 16: 2402
    • 5d Shiosaki M, Inoue M. J. Fluorine Chem. 2015; 175: 160
  • 6 Mei H, Nie C, Acena JL, Soloshonok VA, Roeschenthaler G.-V, Han J. Eur. J. Org. Chem. 2015; 6401
  • 7 Prager JH, Ogden PH. J. Org. Chem. 1968; 33: 2100
  • 8 Han C, Kim EH, Colby DA. J. Am. Chem. Soc. 2011; 133: 5802
  • 9 Prakash GK. S, Zhang Z, Wang F, Munoz S, Olah GA. J. Org. Chem. 2013; 78: 3300
  • 11 Li W, Zhu X, Mao H, Tang Z, Cheng Y, Zhu C. Chem. Commun. 2014; 50: 7521
    • 12a Xie C, Wu L, Mei H, Soloshonok VA, Han J, Pan Y. Tetrahedron Lett. 2014; 55: 5908
    • 12b Xie C, Wu L, Zhou J, Mei H, Soloshonok VA, Han J, Pan Y. J. Fluorine Chem. 2015; 172: 13
    • 12c Xie C, Wu L, Mei H, Soloshonok VA, Han J, Pan Y. Org. Biomol. Chem. 2014; 12: 7836
    • 12d Xie C, Wu L, Han J, Soloshonok VA, Pan Y. Angew. Chem. Int. Ed. 2015; 54: 6019
    • 12e Xie C, Dai Y, Mei H, Han J, Soloshonok VA, Pan Y. Chem. Commun. 2015; 51: 9149
  • 13 Wu C, Li G, Sun W, Zhang M, Hong L, Wang R. Org. Lett. 2014; 16: 1960
    • 14a Saidalimu I, Fang X, He XP, Liang J, Yang XY, Wu FH. Angew. Chem. Int. Ed. 2013; 52: 5566
    • 14b Saidalimu I, Fang X, Lv W, Yang X, He X, Zhang J, Wu FH. Adv. Synth. Catal. 2013; 355: 857
    • 15a Zhang P, Wolf W. J. Org. Chem. 2012; 77: 8840
    • 15b Zhang P, Wolf W. Angew. Chem. Int. Ed. 2013; 52: 7869
  • 16 John JP, Colby DA. J. Org. Chem. 2011; 76: 9163
  • 17 Pravst I, Zupan M, Stavber S. Tetrahedron 2008; 64: 5191
  • 18 The reaction was carried out with 5 equiv of LiBr, 2.5 equiv of K2CO3, and 2 equiv of NBS using THF as solvent at r.t. Complete conversion of 5 was observed within 1 h.
  • 19 The trapping of chlorofluoro-substituted enolates such as 7 with NIS or I2 is also possible, but the corresponding chlorofluoroiodomethyl ketones are considerably less stable than 8 and its analogues.
  • 20 Ramirez F, Desai NB, McKelvie N. J. Am. Chem. Soc. 1962; 84: 1745
  • 21 The Z-isomer was not detected.
    • 22a Burton DJ, Koppes WM. J. Org. Chem. 1975; 40: 3026
    • 22b Eguchi T, Aoyama T, Kakinuma K. Tetrahedron Lett. 1992; 33: 5545