An Efficient Route to Difluoromethylated Pyridines

Kenichi Fujikawa; Akira Kobayashi; Hideki Amii

doi:10.1055/s-0032-1316761

Synthesis, Table of Contents

Synthesis 2012; 44(19): 3015-3018
DOI: 10.1055/s-0032-1316761

paper

An Efficient Route to Difluoromethylated Pyridines

Kenichi Fujikawa

Department of Chemistry and Chemical Biology, Graduate School of Engineering, Gunma University, Kiryu, Gunma 376-8515, Japan, Fax: +81(277)301280 Email: amii@chem-bio.gunma-u.ac.jp

,

Akira Kobayashi

Department of Chemistry and Chemical Biology, Graduate School of Engineering, Gunma University, Kiryu, Gunma 376-8515, Japan, Fax: +81(277)301280 Email: amii@chem-bio.gunma-u.ac.jp

,

Hideki Amii*

Department of Chemistry and Chemical Biology, Graduate School of Engineering, Gunma University, Kiryu, Gunma 376-8515, Japan, Fax: +81(277)301280 Email: amii@chem-bio.gunma-u.ac.jp

› Author Affiliations

Abstract

All articles of this category

Abstract

A convenient route to difluoromethylated pyridines was developed that involves copper-promoted cross-coupling of halopyridines with ethyl difluoro(trimethylsilyl)acetate and subsequent decarboxylation.

Key words

fluorine - pyridines - copper - catalysis - cross-coupling - decarboxylations

Full Text

References

References
1 Scriven EF. V, Toomey Jr JE., Murugan R In Kirk-Othmer Encyclopedia of Chemical Technology . Howe-Grant M. Wiley; New York: 1996. and references therein

2a Hiyama T, Kanie K, Kusumoto T, Morizawa Y, Shimizu M. Organofluorine Compounds: Chemistry and Application . Springer; Berlin: 2000
2b Kirsch P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications. Wiley-VCH; Weinheim: 2004
2c Chambers RD. Fluorine in Organic Chemistry . Blackwell; Oxford: 2004
2d Uneyama K. Organofluorine Chemistry . Blackwell; Oxford: 2006
2e Bégué J.-P, Bonnet-Delpon D. Bioorganic and Medicinal Chemistry of Fluorine . Wiley; Hoboken: 2008
2f Fluorinated Heterocycles, ACS Symposium Series 1003. Gakh AA, Kirk KL. American Chemical Society; Washington DC: 2009
2g Fluorinated Heterocyclic Compounds: Synthesis, Chemistry, and Applications. Petrov VA. Wiley; Hoboken: 2009

3 Hu J, Zhang W, Wang F. Chem. Commun. (Cambridge) 2009; 7465
4 Matsuo M, Tsuji K, Ogino T, Konishi N. EP 554,829, 1993
5 Erickson JA, McLoughlin JI. J. Org. Chem. 1995; 60: 1626

6a Armbruster BL, Molin WT, Bugg MW. Pestic. Biochem. Physiol. 1991; 39: 110
6b Enache AJ, Ilnicki RD. Weed Technol. 1991; 5: 616
6c Feng PC, Solsten RT. Xenobiotica 1991; 21: 1265

7 Feng PC, Solsten RT. Xenobiotica 1994; 24: 729

8a Lee LF. EP 133612, 1985
8b Lee LF, Stikes GL, Molyneaux JM, Sing YL, Chupp JP, Woodard SS. J. Org. Chem. 1990; 55: 2872

9 Goure WF, Leschinsky KL, Wratten SJ, Chupp JP. J. Agric. Food Chem. 1991; 39: 981
10 Katsuyama K, Funabiki K, Matsui M, Muramatsu H, Shibata K. Synlett 1997; 591
11 Iaroshenko VO, Specowius V, Vlach K, Vilches-Herrera M, Ostrovskyi D, Mkrtchyan S, Villinger A, Langer P. Tetrahedron 2011; 67: 5663
12 Fujiwara Y, Dixon JA, Rodriguez RA, Baxter RD, Dixon DD, Collins MR, Blackmond DG, Baran PS. J. Am. Chem. Soc. 2012; 134: 1494

13a Lundgren RJ, Stradiotto M. Angew. Chem. Int. Ed. 2010; 49: 9322
13b Furuya T, Kamlet AS, Ritter T. Nature (London) 2011; 473: 470
13c Roy S, Gregg BT, Gribble GW, Le V.-D, Roy S. Tetrahedron 2011; 67: 2161
13d Tomashenko OA, Grushin VV. Chem. Rev. 2011; 111: 4475 ; and references therein

14a Oishi M, Kondo H, Amii H. Chem. Commun. (Cambridge) 2009; 1909
14b Kondo H, Oishi M, Fujikawa K, Amii H. Adv. Synth. Catal. 2011; 353: 1247

15 Fujikawa K, Fujioka Y, Kobayashi A, Amii H. Org. Lett. 2011; 13: 5560
16 Recently, Hartwig and co-worker succeeded in the development of a straightforward method for aromatic difluoromethylation of electron-neutral, electron-rich aryl iodides using HCF₂SiMe₃: Fier PF, Hartwig JF. J. Am. Chem. Soc. 2012; 134: 5524

For the catalytic introduction of difluoroacetate moieties onto aryl rings, see:

17a Taguchi T, Kitagawa O, Morikawa T, Nishiwaki T, Uehara H, Endo H, Kobayashi Y. Tetrahedron Lett. 1986; 27: 6103
17b Sato K, Kawata R, Ama F, Omote M, Ando A, Kumadaki I. Chem. Pharm. Bull. 1999; 47: 1013
17c Ashwood MS, Cottrell IF, Cowden CJ, Wallace DJ, Davies AJ, Kennedy DJ, Dolling UH. Tetrahedron Lett. 2002; 43: 9271
17d Murakami S, Ishi H, Tajima T, Fuchigami T. Tetrahedron 2006; 62: 3761
17e Araki K, Inoue M. JP 2010116363, 2010
17f Ohtsuka Y, Yamakawa T. Tetrahedron 2011; 67: 2323

18a Uneyama K, Mizutani G, Maeda K, Kato T. J. Org. Chem. 1999; 64: 6717
18b Amii H, Kobayashi T, Uneyama K. Synthesis 2000; 2001
18c Clavel P, Biran C, Bordeau M, Roques N, Trévin S. Tetrahedron Lett. 2000; 41: 8763
18d Utsumi S, Katagiri T, Uneyama K. Tetrahedron 2012; 68: 580

19a Hall A, Billinton A, Brown SH, Clayton NM. Chowdhury A, Giblin GM. P, Goldsmith P, Hayhow TG, Hurst DN, Kilford IR, Naylor A, Passingham B, Winyard L. Bioorg. Med. Chem. Lett. 2008; 18: 3392
19b Kreutter KD, Lu T, Lee L, Giardino EC, Patel S, Huang H, Xu G, Fitzgerald M, Haertlein BJ, Mohan V, Crysler C, Eisennagel S, Dasgupta M, McMillan M, Spurlino JC, Huebert ND, Maryanoff BE, Tomczuk BE, Damiano BP, Player MR. Bioorg. Med. Chem. Lett. 2008; 18: 2865

20 Eto H, Kaneko Y, Sakamoto T. Chem. Pharm. Bull. 2000; 48: 982
21 Kuduk SD, Beshore DC, Dimarco CN, Greshock TJ. WO 2011084371, 2011

22a Chassaing CP. A, Thorsten M. WO 2010146083, 2010
22b Moritani Y, Imashiro N, Sato A. JP 2008285481, 2008

23 Uneyama K, Takagi J, Fujitani K. JP 2008266242, 2008
24 Mori T, Iwai Y, Ichikawa J. Chem. Lett. 2005; 34: 778