Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2015; 26(13): 1835-1840
DOI: 10.1055/s-0034-1380441
DOI: 10.1055/s-0034-1380441
letter
One-Pot Synthesis of α-Fluoroketones and 3-Fluoro-2,4-diarylfurans from Trifluoromethyl β-Diketones via Decarboxylation
Further Information
Publication History
Received: 17 April 2015
Accepted after revision: 17 May 2015
Publication Date:
09 July 2015 (online)
![](https://www.thieme-connect.de/media/synlett/201513/lookinside/thumbnails/st-2015-w0268-l_10-1055_s-0034-1380441-1.jpg)
Abstract
A facile and mild one-pot protocol via decarboxylation of trifluoromethyl β-diketones has been developed for the construction of α-fluoroketones and 3-fluoro-2,4-diarylfurans which are important units in many biologically active compounds and useful precursors in a variety of functional-group transformations.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380441.
- Supporting Information
-
References and Notes
- 1a Jeschke P. Science 2010; 66: 10
- 1b O’Hagan D. Chem. Soc. Rev. 2008; 37: 308
- 1c Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
- 1d Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
- 1e Chambers RD. Fluorine in Organic Chemistry . Blackwell Publishing; Oxford: 2004
- 1f Fluorine in Medicinal Chemistry and Chemical Biology. Ojima I. Wiley-Blackwell; Oxford: 2009
- 2 Ilardi EA, Vitaku E, Njardarson JT. J. Med. Chem. 2014; 57: 2832
- 3a Thvedt TH. K, Fuglseth E, Sundby E, Hoff BH. Tetrahedron 2010; 66: 6733
- 3b Malamakal RM, Hess WR, Davis TA. Org. Lett. 2010; 12: 2186
- 4a Borzecka W, Lavandera I, Gotor V. J. Org. Chem. 2013; 78: 7312
- 4b Fuglseth E, Sundby E, Hoff BH. J. Fluorine Chem. 2009; 130: 600
- 4c Mohanta PK, Davis TA, Gooch JR, Flowers RA. J. Am. Chem. Soc. 2005; 127: 11896
- 4d Matsuda T, Harada T, Nakamura K. Chem. Commun. 2000; 1367
- 5a He Y, Zhang X, Shen N, Fan X. J. Fluorine Chem. 2013; 156: 9
- 5b Lawrence NJ, Patterson RP, Ooi LL, Cook D, Ducki S. Bioorg. Med. Chem. Lett. 2006; 16: 5844
- 5c Heinrich MR. Tetrahedron Lett. 2007; 48: 3895
- 6 Furuya T, Kuttruff CA, Ritter T. Curr. Opin. Drug Discovery Dev. 2008; 11: 803
- 7a Liu J, Chan J, Bryant CM, Duspara PA, Lee EE, Powell D, Yang H, Liu Z, Walpole C, Roberts E, Batey RA. Tetrahedron Lett. 2012; 53: 2971
-
7b Yi WB, Huang X, Cai C, Zhang W. Green Chem. 2012; 14: 3185
- 7c Kwiatkowski P, Beeson TD, Conrad JC, MacMillan DW. C. J. Am. Chem. Soc. 2011; 133: 1738
- 7d Ahlsten N, Bartoszewicz A, Agrawal S, Martín-Matute B. Synthesis 2011; 2600
- 7e Fuglseth E, Thvedt TH. K, Møll MF, Hoff BH. Tetrahedron 2008; 64: 7318
- 7f Stavber S, Jereb M, Zupan M. Chem. Commun. 2000; 1323
- 7g Peng W, Shreeve JM. J. Org. Chem. 2005; 70: 5760
- 7h Thvedt TH. K, Fuglseth E, Sundby E, Hoff BH. Tetrahedron 2009; 65: 9550
- 7i Stavber G, Zupan M, Stavber S. Synlett 2009; 589
- 8a He Y, Zhang X, Shen N, Fan X. J. Fluorine Chem. 2013; 156: 9
- 8b Chen ZZ, Zhu W, Zheng ZB, Zou XZ. J. Fluorine Chem. 2010; 131: 340
- 8c Makosza M, Bujok R. Tetrahedron Lett. 2004; 45: 1385
- 8d Kim DW, Song CE, Chi DY. J. Am. Chem. Soc. 2002; 124: 10278
- 8e Wagner PJ, Thomas MJ, Puchalski AE. J. Am. Chem. Soc. 1986; 108: 7739
- 8f Liotta CL, Harris HP. J. Am. Chem. Soc. 1974; 96: 2250
- 8g Fitjer L. Synthesis 1977; 189
- 8h Leroy J. J. Org. Chem. 1981; 46: 206
- 9a Lipshutz BH. Chem. Rev. 1986; 86: 795
- 9b Dean FM In Advances in Heterocyclic Chemistry . Vol. 31. Katritzky AR. Academic Press; New York: 1983: 273
- 9c Natural Products Chemistry. Vol. 1–3. Nakanishi K, Goto T, Ito S, Natori S, Nozoe S. Kodansha; Tokyo: 1974
- 10a Paal C. Ber. Dtsch. Chem. Ges. 1884; 17: 2756
- 10b Knorr L. Ber. Dtsch. Chem. Ges. 1884; 17: 2863
- 11a Feist F. Ber. Dtsch. Chem. Ges. 1902; 35: 1545
- 11b Benary E. Ber. Dtsch. Chem. Ges. 1911; 44: 489
- 12 Ma YH, Zhang S, Yang SP, Song FJ, You JS. Angew. Chem. Int. Ed. 2014; 53: 7870
- 13 Bronnert DL. E, Saunders BC. Tetrahedron 1965; 21: 3325
- 14 Arimitsu S, Jacobsen JM, Hammond GB. J. Org. Chem. 2008; 73: 2886
- 15a Saidalium I, Fang X, Lv WW, Yang XY, He XP, Zhang JY, Wu FH. Adv. Synth. Catal. 2013; 355: 857
- 15b Saidalium I, Fang X, He XP, Liang J, Yang XY, Wu FH. Angew. Chem. Int. Ed. 2013; 52: 5566
- 16a Sloop JC, Boyle PD, Fountain AW, Pearman WF, Swann JA. Eur. J. Org. Chem. 2011; 936
- 16b Sloop JC, Bumgardner CL, Washington G, Loehle WD, Sankar SS, Lewis AB. J. Fluorine Chem. 2006; 127: 780
- 17 Typical Experimental Procedure for the Synthesis of 2 from 1 To a mixture of 1d (146 mg, 0.5 mmol) and Na2CO3 (159 mg, 1.5 mmol) in MeCN (0.3 mL) and H2O (0.1 mL), a solution of Selectfluor (212 mg, 0.6 mmol) in MeCN (0.3 mL) and H2O (0.3 mL) was added over 30 min at 0 °C. The reaction mixture was then stirred for 8 h at 0 °C. When the reaction was complete (monitored by TLC), sat. aq NH4Cl (4 mL) was added to quench the reaction. After extraction with CH2Cl2 and drying with Na2SO4, the organic layer was concentrated under reduced pressure, and the residue was purified by column chromatography on silica gel using hexane–EtOAc (20:1) as eluent to afford the desired products 2d (64 mg, 60%). 1-[(1,1′-Biphenyl)-4-yl]-2-fluoroethanone (2d) White solid; mp 131.5–132.4 °C. 1H NMR (400 MHz, CDCl3): δ = 7.98 (d, J = 8.0 Hz, 2 H), 7.73–7.71 (m, 2 H), 7.64–7.62 (m, 2 H), 7.51–7.47 (m, 2 H), 7.44–7.40 (m, 1 H), 5.56 (d, J = 48.0 Hz, 2 H). 13C NMR (101 MHz, CDCl3): δ = 193.0 (d, J = 15.2 Hz), 146.8, 139.5, 132.3, 129.0, 128.5, 128.4 (d, J = 2.0 Hz), 127.4, 127.2, 83.7 (d, J = 183.8 Hz). 19F NMR (376 MHz, CDCl3): δ = –230.28 (t, J = 48.8 Hz, 1 F). IR (KBr): ν = 3380, 2929, 2851, 1700, 1602, 1407, 1241, 1207, 1091, 975, 766, 691 cm–1. MS (EI): m/z = 214, 182, 181 (100), 152, 76, 51. HRMS: m/z calcd for [C14H11FO]+: 214.0794; found: 214.0795.
- 18 Typical Experimental Procedure for the Synthesis of 3 from 1 To a mixture of 1a (108 mg, 0.5 mmol) and NaOH (80 mg, 2.0 mmol) in MeCN (0.2 mL) and H2O (0.1 mL), a solution of Selectfluor (212 mg, 0.6 mmol) in MeCN (0.3 mL) and H2O (0.1 mL) was added slowly at 0 °C. The reaction mixture was stirred for 3 h at 0 °C. It was then heated for 6 h at 50 °C. When the reaction was complete (monitored by TLC), sat. aq NH4Cl (6 mL) was added to quench the reaction. After extraction with EtOAc and drying with Na2SO4, the organic layer was concentrated under reduced pressure, and the residue was purified by column chromatography on silica gel using hexane–EtOAc (60:1 to 30:1) as eluent to afford the desired products 3a (40 mg, 67%). 3-Fluoro-2,4-diphenylfuran (3a) White solid; mp 78.4–79.0 °C. 1H NMR (400 MHz, CDCl3) δ = 7.75 (d, J = 8.0 Hz, 2 H), 7.60 (d, J = 8.0 Hz, 2 H), 7.54 (d, J = 4.0 Hz, 1 H), 7.46–7.41 (m, 4 H), 7.36–7.29 (m, 2 H). 13C NMR (101 MHz, CDCl3): δ = 147.5 (d, J = 256.5 Hz), 137.7 (d, J = 21.2 Hz), 136.3 (d, J = 7.1 Hz), 129.3 (d, J = 3.0 Hz), 128.9 (d, J = 3.0 Hz), 128.8, 128.7, 127.7, 127.3, 126.5 (d, J = 3.0 Hz), 123.5 (d, J = 6.0 Hz), 119.4 (d, J = 14.1 Hz). 19F NMR (376 MHz, CDCl3): δ = –166.91 (d, J = 3.7 Hz, 1 F). IR (KBr): ν = 3422, 3151, 2923, 2852, 1948, 1879, 1634, 1496, 1443, 1410, 1066, 908, 759, 747, 690 cm–1. MS (EI): m/z = 238 (100), 209, 133, 105, 91, 77, 44. HRMS: m/z calcd for [C16H11FO]+: 238.0794; found: 238.0795.