Citation: Tesfaye Tebeka Simur, Tian Ye, You-Jie Yu, Feng-Lian Zhang, Yi-Feng Wang. C–F bond functionalizations of trifluoromethyl groups via radical intermediates[J]. Chinese Chemical Letters, ;2022, 33(3): 1193-1198. doi: 10.1016/j.cclet.2021.08.043 shu

C–F bond functionalizations of trifluoromethyl groups via radical intermediates

Department of Chemistry, University of Science and Technology of China, Hefei 230026, China

zfl9@ustc.edu.cn

yfwangzj@ustc.edu.cn

Received Date: 18 June 2021
Revised Date: 7 August 2021
Accepted Date: 8 August 2021
Available Online: 12 August 2021

Figures(16)

Selective functionalization of C–F bonds in trifluoromethyl groups has recently received a growing interest, as it offers atom- and step-economic pathways to access highly valuable mono- and difluoroalkyl-substituted organic molecules using simple and inexpensive trifluoromethyl sources as the starting materials. In this regard, impressive progress has been made on the defluorinative functionalization reactions that proceed via radical intermediates. Nevertheless, it is still a great challenge to precisely control the defluorination process, due to the continuous decrease of the C–F bond strength after the replacement of one or two fluorine atoms with various functionalities. This review article is aimed to provide a brief overview of recently reported methods used to functionalize C–F bonds of CF₃ groups via radical intermediates. An emphasis is placed on the discussion of mechanistic aspects and synthetic applications
- C–F bond functionalizations,
- Radical intermediates,
- Trifluoromethyl groups,
- Difluorinated compounds,
- Monofluorinated compounds
1. [1]
  E.P. Gillis, K.J. Eastman, M.D. Hill, D.J. Donnelly, N.A. Meanwell, J. Med. Chem. 58 (2015) 8315-8359. doi: 10.1021/acs.jmedchem.5b00258
2. [2]
  J. Wang Y. Zhou, Z. Gu, et al., Chem. Rev. 116 (2016) 422-518. doi: 10.1021/acs.chemrev.5b00392
3. [3]
  T. Fujiwara, D. O'Hagan, J. Fluorine Chem. 167 (2014) 16-29. doi: 10.1016/j.jfluchem.2014.06.014
4. [4]
  R. Berger, G. Resnati, P. Metrangolo, E. Weber, J. Hulliger, Chem. Soc. Rev. 40 (2011) 3496-3508. doi: 10.1039/c0cs00221f
5. [5]
  W.K. Hagmann, J. Med. Chem. 51 (2008) 4359-4369. doi: 10.1021/jm800219f
6. [6]
  D. O'Hagan, Chem. Soc. Rev. 37 (2008) 308-319. doi: 10.1039/B711844A
7. [7]
  T. Furuya, A.S. Kamlet, T. Ritter, Nature 473 (2011) 470-477. doi: 10.1038/nature10108
8. [8]
  X. Yang, T. Wu, R.J. Phipps, F.D. Toste, Chem. Rev. 115 (2015) 826-870. doi: 10.1021/cr500277b
9. [9]
  C. Ni, M. Hu, J. Hu, Chem. Rev. 115 (2015) 765-825. doi: 10.1021/cr5002386
10. [10]
  Z. Feng, Y.L. Xiao, X. Zhang, Acc. Chem. Res. 51 (2018) 2264-2278. doi: 10.1021/acs.accounts.8b00230
11. [11]
  V. Rauniyar, A.D. Lackner, G.L. Hamilton, F.D. Toste, Science 334 (2011) 1681-1684. doi: 10.1126/science.1213918
12. [12]
  H. Amii, K. Uneyama, Chem. Rev. 109 (2009) 2119-2183. doi: 10.1021/cr800388c
13. [13]
  T. Ahrens, J. Kohlmann, M. Ahrens, T. Braun, Chem. Rev. 115 (2015) 931-972. doi: 10.1021/cr500257c
14. [14]
  X. Ma, Q. Song, Chem. Soc. Rev. 49 (2020) 9197-9219. doi: 10.1039/D0CS00604A
15. [15]
  S. Barata-Vallejo, A. Postigo, Chem. Eur. J. 26 (2020) 11065-11084. doi: 10.1002/chem.202000856
16. [16]
  R.P. Bhaskaran, B.P. Babu, Adv. Synth. Catal. 362 (2020) 5219-5237. doi: 10.1002/adsc.202000996
17. [17]
  G.K. Surya Prakash, J. Hu, G.A. Olah, J. Fluorine Chem. 112 (2001) 355-360. doi: 10.1016/S0022-1139(01)00535-8
18. [18]
  J. Wettergren, T. Ankner, G. Hilmersson, Chem. Commun. 46 (2010) 7596-7598. doi: 10.1039/c0cc02009e
19. [19]
  H. Iwamoto, H. Imiya, M. Ohashi, S. Ogoshi, J. Am. Chem. Soc. 142 (2020) 19360-19367. doi: 10.1021/jacs.0c09639
20. [20]
  L. Zhou, D. Anand, Visible light-mediated C-F bond activation, in: A. Postigo (Ed.), Late-Stage Fluorination of Bioactive Molecules and Biologically-Relevant Substrates, Elsevier, Amsterdan, 2019, pp. 159-181.
21. [21]
  F. Jaroschik, Chem. Eur. J. 24 (2018) 14572-14582. doi: 10.1002/chem.201801702
22. [22]
  J. Mattay, J. Runsink, T. Rumbach, C. Ly, J. Gersdorf, J. Am. Chem. Soc. 107 (1985) 2557-2558. doi: 10.1021/ja00294a063
23. [23]
  M. Kako, T. Morita, T. Torihara, Y. Nakadaira, J. Chem. Soc., Chem. Commun. (1993) 678-680.
24. [24]
  B.E. Smart, J. Fluorine Chem. 109 (2001) 3-11. doi: 10.1016/S0022-1139(01)00375-X
25. [25]
  H. Senboku, Y. Yamauchi, T. Fukuhara, S. Hara, Synlett (2008) 438-442 2008.
26. [26]
  L.N. Henning, J. Jensen, Acta Chem. Scand. (1974) 263-265 28b.
27. [27]
  H. Amii, Y. Hatamoto, M. Seo, K. Uneyama, J. Org. Chem. 66 (2001) 7216-7218. doi: 10.1021/jo015720i
28. [28]
  K. Uneyama, H. Amii, J. Fluorine Chem. 114 (2002) 127-131. doi: 10.1016/S0022-1139(02)00039-8
29. [29]
  H. Amii, R. Hayashi, M. Seo, et al., J. Fluorine Chem. 152 (2013) 90-93. doi: 10.1016/j.jfluchem.2013.04.001
30. [30]
  S.B. Munoz, C. Ni, Z. Zhang, et al., Eur. J. Org. Chem. (2017) 2322-2326 2017.
31. [31]
  K. Chen, N. Berg, R. Gschwind, B. König, J. Am. Chem. Soc. 139 (2017) 18444-18447. doi: 10.1021/jacs.7b10755
32. [32]
  X. Yuan, K.Q. Zhuang, Y.S. Cui, et al., Commun. Chem. 3 (2020) 98. doi: 10.1038/s42004-020-00354-5
33. [33]
  H. Wang, N.T. Jui, J. Am. Chem. Soc. 140 (2018) 163-166. doi: 10.1021/jacs.7b12590
34. [34]
  D.B. Vogt, C.P. Seath, H. Wang, N.T. Jui, J. Am. Chem. Soc. 141 (2019) 13203-13211. doi: 10.1021/jacs.9b06004
35. [35]
  C.M. Hendy, G.C. Smith, Z. Xu, T. Lian, N.T. Jui, J. Am. Chem. Soc. 143 (2021) 8987-8992. doi: 10.1021/jacs.1c04427
36. [36]
  J.B.I. Sap, N.J.W. Straathof, T. Knauber, et al., J. Am. Chem. Soc. 142 (2020) 9181-9187. doi: 10.1021/jacs.0c03881
37. [37]
  C. Luo, J.S. Bandar, J. Am. Chem. Soc. 141 (2019) 14120-14125. doi: 10.1021/jacs.9b07766
38. [38]
  N. Sugihara, K. Suzuki, Y. Nishimoto, M. Yasuda, J. Am. Chem. Soc. 143 (2021) 9308-9313. doi: 10.1021/jacs.1c03760
39. [39]
  T. Xiao, L. Li, L. Zhou, J. Org. Chem. 81 (2016) 7908-7916. doi: 10.1021/acs.joc.6b01620
40. [40]
  S.B. Lang, R.J. Wiles, C.B. Kelly, G.A. Molander, Angew. Chem. Int. Ed. 56 (2017) 15073-15077. doi: 10.1002/anie.201709487
41. [41]
  J. Qi, F.L. Zhang, J.K. Jin, et al., Angew. Chem. Int. Ed. 59 (2020) 12876-12884. doi: 10.1002/anie.201915619
42. [42]
  P.J. Xia, D. Song, Z.P. Ye, et al., Angew. Chem. Int. Ed. 59 (2020) 6706-6710. doi: 10.1002/anie.201913398
43. [43]
  W. Xu, H. Jiang, J. Leng, H.W. Ong, J. Wu, Angew. Chem. Int. Ed. 59 (2020) 4009-4016. doi: 10.1002/anie.201911819
44. [44]
  H. Xu, Z. Jiang, Chin. J. Org. Chem. 40 (2020) 3483-3484. doi: 10.6023/cjoc202000069
45. [45]
  N. Zhou, X.A. Yuan, Y. Zhao, J. Xie, C. Zhu, Angew. Chem. Int. Ed. 57 (2018) 3990-3994. doi: 10.1002/anie.201800421
46. [46]
  N.V. Moskalev, S.P. Zhuravkov, V.D. Ogorodnikov, Russ. Chem. Bull. 45 (1996) 2461-2461. doi: 10.1007/BF01435407
47. [47]
  K. Uneyama, G. Mizutani, K. Maeda, T. Kato, J. Org. Chem. 64 (1999) 6717-6723. doi: 10.1021/jo990571d
48. [48]
  Y.J. Yu, F.L. Zhang, T.Y. Peng, et al., Science 371 (2021) 1232-1240. doi: 10.1126/science.abg0781
49. [49]
  D. Ge, X. Chu, Chin. J. Org. Chem. 41 (2021) 2150-2151.
50. [50]
  T.W. Butcher, J.L. Yang, W.M. Amberg, et al., Nature 583 (2020) 548-553. doi: 10.1038/s41586-020-2399-1
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2. [2]
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3. [3]
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4. [4]
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