Efficient Synthesis of α,α-Difluoro Ketones Using SelectfluorTM F-TEDA-BF4

Igor Pravst; Marko Zupan; Stojan Stavber

doi:10.1055/s-2005-918424

PAPER

Efficient Synthesis of α,α-Difluoro Ketones Using Selectfluor^TM F-TEDA-BF₄

Igor Pravst^a, Marko Zupan^a,b, Stojan Stavber*^b
^a Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000 Ljubljana, Slovenia
^b Laboratory for Organic and Bioorganic Chemistry, ‘Jozef Stefan’ Institute, Jamova 39, 1000 Ljubljana, Slovenia
e-Mail: stojan.stavber@ijs.si;

Abstract

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Abstract

Selective and efficient synthesis of α,α-difluoro ketones was achieved following a protocol which includes the transformation of α-methylene ketones to the corresponding n-butylimine derivatives and their further treatment with Selectfluor^TM F-TEDA-BF₄ in acetonitrile solution at 80 °C.

Key words

halogenation - fluorination - imines - ketones - α,α-difluoro ketones - Selectfluor F-TEDA-BF₄

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References

1 Smart BE. J. Fluorine Chem. 2001, 109: 3

2a Chemistry of Organic Fluorine Compounds II: A Critical Review, ACS Monograph 187 Hudlicky M. Pavlath AE. American Chemical Society; Washington, DC: 1995.

2b Modern Fluoroorganic Chemistry. Synthesis, Reactivity, Applications Kirsch P. Wiley-VCH; Weinheim: 2004.

2c Chambers RD. Fluorine in Organic Chemistry Blackwell; Oxford: 2004.

2d ChemBioChem, Special Issue on Fluorine in Life Sciences Vol. 37: Royal Society of Chemistry; Cambridge: 2004. p.557-726

3 Methods of Organic Chemistry (Houben-Weyl), Organofluorine Compounds Baasner B. Hagemann H. Tatlow JC. Vol. E 10a-c; Thieme: Stuttgart: 1999.

4 Shimizu M. Hiyama T. Angew. Chem. Int. Ed. 2005, 44: 214

5 Gelb MH. Svaren JP. Abeles RH. Biochemistry 1985, 24: 1813

6 Tarnus C. Jung MJ. Remy JM. Baltzer S. Schirlin DG. FEBS Lett. 1989, 249: 47

7 Sham HL. Stein H. Rempel CA. Cohen J. Plattner JJ. FEBS Lett. 1987, 220: 299

8 Thaisrivongs S. Pals DT. Kati WM. Turner SR. Thomasco LM. Watt W. J. Med. Chem. 1986, 29: 2080

9 Takahashi LH. Radhakrishnan R. Rosenfield RE. Meyer EF. Trainor DA. J. Am. Chem. Soc. 1989, 111: 3368

10 Imperiali B. Abeles RH. Biochemistry 1987, 26: 4474

11 Imperiali B. Abeles RH. Biochemistry 1986, 25: 3760

12 Robinson RP. Donahue KM. J. Org. Chem. 1992, 57: 7309

13 Sham HL. Betebenner DA. Wideburg NE. Kempf DJ. Plattner JJ. Norbeck DW. J. Fluorine Chem. 1995, 73: 221

14 Wolfe MS. Xia WM. Moore CL. Leatherwood DD. Ostaszewski B. Rahmati T. Donkor IO. Selkoe DJ. Biochemistry 1999, 38: 4720

15 Moore CL. Leatherwood DD. Diehl TS. Selkoe DJ. Wolfe MS. J. Med. Chem. 2000, 43: 3434

16 Wolfe MS. Citron M. Diehl TS. Xia WM. Donkor IO. Selkoe DJ. J. Med. Chem. 1998, 41: 6

17 Reiter LA. Martinelli GJ. Reeves LA. Mitchell PG. Bioorg. Med. Chem. Lett. 2000, 10: 1581

18 Biomedical Frontiers of Fluorine Chemistry Ojima I. McCarthy JR. Wolfe MS. American Chemical Society; Washington DC: 1996.

19 Stavber S. Zupan M. J. Org. Chem. 1987, 52: 5022

20 Zupan M. Iskra J. Stavber S. J. Org. Chem. 1995, 60: 259

21 Stavber S. Zupan M. Synlett 1996, 693

22 Zajc B. Zupan M. J. Org. Chem. 1982, 47: 573

23 Umemoto T. Fukami S. Tomizawa G. Harasawa K. Kawada K. Tomita K. J. Am. Chem. Soc. 1990, 112: 8563

24 Xu ZQ. DesMarteau DD. Gotoh Y. J. Fluorine Chem. 1992, 58: 71

25 Davis FA. Han W. Murphy CK. J. Org. Chem. 1995, 60: 4730

26 Banks RE. Lawrence NJ. Popplewell AL. J. Chem. Soc., Chem. Commun. 1994, 343

27 Stavber G. Zupan M. Jereb M. Stavber S. Org. Lett. 2004, 6: 4973

28 Stavber S. Jereb M. Zupan M. Synthesis 2002, 2609

29 Tozer MJ. Herpin TF. Tetrahedron 1996, 52: 8619

30 Stavber S. Jereb M. Zupan M. Chem. Commun. 2000, 1323

31a Nakano T. Makino M. Morizawa Y. Matsumura Y. Angew. Chem. Int. Ed. 1996, 35: 1019

31b Thomas MG. Suckling CJ. Pitt AR. Suckling KE. J. Chem. Soc., Perkin Trans.1 1999, 3191

32 Ying WW. DesMarteau DD. Gotoh Y. Tetrahedron 1996, 52: 15

33 Peng W. Shreeve JM. J. Org. Chem. 2005, 70: 5760

34 Gutman AL. Etinger M. Nisnevich G. Polyak F. Tetrahedron: Asymmetry 1998, 9: 4369

35 Johnson GP. Marples BA. Tetrahedron Lett. 1984, 25: 3359

36 Warmuth R. Munsch TE. Stalker RA. Li B. Beatty A. Tetrahedron 2001, 57: 6383

37 Gilicinski AG. Pez GP. Syvret RG. Lal GS. J. Fluorine Chem. 1992, 59: 157

38 Singh RP. Shreeve JM. Acc. Chem. Res. 2004, 37: 31

39 Stavber S. Zupan M. Acta Chim. Slov. 2005, 52: 13

40 Appelman EH. Basile LJ. Thompson RC. J. Am. Chem. Soc. 1979, 101: 3384