Download PDF
Synlett 2021; 32(14): 1379-1384
DOI: 10.1055/a-1479-8264
synpacts

Transition-Metal-Catalyzed Alkylation of Polyfluoroarenes through C–F Bond Cleavage

Qian Zhang
a   Jilin Province Key Laboratory of Organic Functional Molecular Design and Synthesis, Department of Chemistry, Northeast Normal University, Changchun 130024, P. R. of China
,
Tao Xiong  ∗
a   Jilin Province Key Laboratory of Organic Functional Molecular Design and Synthesis, Department of Chemistry, Northeast Normal University, Changchun 130024, P. R. of China
,
Qian Zhang∗
a   Jilin Province Key Laboratory of Organic Functional Molecular Design and Synthesis, Department of Chemistry, Northeast Normal University, Changchun 130024, P. R. of China
b   State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China
› Author AffiliationsThe authors thank the National Natural Science Foundation of China (grants nos. 21831002 and 21672033), the Fundamental Research Funds for the Central Universities, and the Ten Thousand Talents Program for their generous financial support.
› Further Information
    Permissions and Reprints All articles of this category


Abstract

The polyfluoroarenes are a subgroup of organofluorines that are widely utilized in both medicinal chemistry and materials science. We briefly summarize recent advances in the synthesis of these important compounds, with particular attention to our recent CuH-catalyzed defluorinative alkylation of polyfluoroarenes with alkenes in a highly site-selective C–F bond-cleavage fashion.

1 Introduction

2 Transition-Metal-Catalyzed Alkylation through Selective C–F Bond Cleavage

3 CuH-Catalyzed Defluorinative Alkylation of Polyfluoroarenes with Alkenes

4 Summary and Outlook

Key words

polyfluoroarenes - C–F bond cleavage - copper catalysis - alkylation - alkenes


Publication History

Received: 05 April 2021

Accepted: 12 April 2021

Accepted Manuscript online:
12 April 2021

Article published online:
28 April 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References

    • 1a Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
      CrossrefPubMed
    • 1b O’Hagan D. Chem. Soc. Rev. 2008; 37: 308
      CrossrefPubMed
    • 1c Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
      CrossrefPubMed
    • 1d Jeschke P. ChemBioChem 2004; 5: 570
      CrossrefPubMed
    • 1e Ametamey SM, Honer M, Schubiger PA. Chem. Rev. 2008; 108: 1501
      CrossrefPubMed
    • 1f Cametti M, Crousse B, Metrangolo P, Milani R, Resnati G. Chem. Soc. Rev. 2012; 41: 31
      CrossrefPubMed
    • 1g Berger R, Resnati G, Metrangolo P, Weber E, Hulliger J. Chem. Soc. Rev. 2011; 40: 3496
      CrossrefPubMed
    • 2a Brown JM, Gouverneur V. Angew. Chem. Int. Ed. 2009; 48: 8610
      CrossrefPubMed
    • 2b Furuya T, Kamlet AS, Ritter T. Nature 2011; 473: 470
    • 2c Liang T, Neumann CN, Ritter T. Angew. Chem. Int. Ed. 2013; 52: 8214
      CrossrefPubMed
    • 2d Campbell MG, Ritter T. Chem. Rev. 2015; 115: 612
      CrossrefPubMed
    • 2e Preshlock S, Tredwell M, Gouverneur V. Chem. Rev. 2016; 116: 719
      CrossrefPubMed
    • 3a Weck M, Dunn AR, Matsumoto K, Coates GW, Lobkovsky EB, Grubbs RH. Angew. Chem. Int. Ed. 1999; 38: 2741
      CrossrefPubMed
    • 3b Sakamoto Y, Suzuki T, Miura A, Fujikawa H, Tokito S, Taga Y. J. Am. Chem. Soc. 2000; 122: 1832
      Crossref
    • 3c Nitschke JR, Tilley TD. J. Am. Chem. Soc. 2001; 123: 10183
      CrossrefPubMed
    • 3d Tsuzuki T, Shirasawa N, Suzuki T, Tokito S. Adv. Mater (Weinheim, Ger.) 2003; 15: 1455
      Crossref
    • 3e Meyer EA, Castellano RK, Diederich F. Angew. Chem. Int. Ed. 2003; 42: 1210
      CrossrefPubMed
    • 3f Babudri F, Farinola GM, Naso F, Ragni R. Chem. Commun. 2007; 1003
      PubMed
    • 4a Lafrance M, Rowley CN, Woo TK, Fagnou K. J. Am. Chem. Soc. 2006; 128: 8754
      CrossrefPubMed
    • 4b Do H.-Q, Daugulis O. J. Am. Chem. Soc. 2008; 130: 1128
      CrossrefPubMed
    • 4c Simonetti M, Perry GJ. P, Cambeiro XC, Juliá-Hernández F, Arokianathar JN, Larrosa I. J. Am. Chem. Soc. 2016; 138: 3596
      CrossrefPubMed
    • 4d Li W, Yuan D, Wang G, Zhao Y, Xie J, Li S, Zhu C. J. Am. Chem. Soc. 2019; 141: 3187
      CrossrefPubMed
    • 5a Zhang X, Fan S, He C.-Y, Wan X, Min Q.-Q, Yang J, Jiang Z.-X. J. Am. Chem. Soc. 2010; 132: 4506
      CrossrefPubMed
    • 5b Nett AJ, Zhao W, Zimmerman PM, Montgomery J. J. Am. Chem. Soc. 2015; 137: 7636
      CrossrefPubMed
  • 6 Wei Y, Zhao H, Kan J, Su W, Hong M. J. Am. Chem. Soc. 2010; 132: 2522
    CrossrefPubMed
    • 7a Fan S, Chen F, Zhang X. Angew. Chem. Int. Ed. 2011; 50: 5918
      CrossrefPubMed
    • 7b Yao T, Hirano K, Satoh T, Miura M. Angew. Chem. Int. Ed. 2011; 50: 2990
      CrossrefPubMed
    • 7c Xie W, Chang S. Angew. Chem. Int. Ed. 2016; 55: 1876
      CrossrefPubMed
    • 8a Fan S, He C.-Y, Zhang X. Chem. Commun. 2010; 46: 4926
      CrossrefPubMed
    • 8b Sun Z.-M, Zhang J, Manan RS, Zhao P. J. Am. Chem. Soc. 2010; 132: 6935
      CrossrefPubMed
    • 8c Xu S, Wu G, Ye F, Wang X, Li H, Zhao X, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2015; 54: 4669
      CrossrefPubMed
    • 8d Xie W, Heo J, Kim D, Chang S. J. Am. Chem. Soc. 2020; 142: 7487
      CrossrefPubMed
  • 9 Xie W, Yoon JH, Chang S. J. Am. Chem. Soc. 2016; 138: 12605
    CrossrefPubMed
    • 10a Meier G, Braun T. Angew. Chem. Int. Ed. 2009; 48: 1546
      CrossrefPubMed
    • 10b Clot E, Eisenstein O, Jasim N, Macgregor SA, McGrady JE, Perutz RN. Acc. Chem. Res. 2011; 44: 333
      CrossrefPubMed
    • 10c Kuehnel MF, Lentz D, Braun T. Angew. Chem. Int. Ed. 2013; 52: 3328
      CrossrefPubMed
    • 10d Aizenberg M, Milstein D. Science 1994; 265: 359
      CrossrefPubMed
    • 10e Aizenberg M, Milstein D. J. Am. Chem. Soc. 1995; 117: 8674
      Crossref
    • 10f Schaub T, Fischer P, Steffen A, Braun T, Radius U, Mix A. J. Am. Chem. Soc. 2008; 130: 9304
      CrossrefPubMed
    • 10g Lv H, Zhan J.-H, Cai Y.-B, Yu Y, Wang B, Zhang J.-L. J. Am. Chem. Soc. 2012; 134: 16216
      CrossrefPubMed
    • 10h Fischer P, Götz K, Eichhorn A, Radius U. Organometallics 2012; 31: 1374
      Crossref
    • 10i Zhan J.-H, Lv HB, Yu Y, Zhang J.-L. Adv. Synth. Catal. 2012; 354: 1529
      Crossref
    • 10j Lv HB, Cai Y.-B, Zhang J.-L. Angew. Chem. Int. Ed. 2013; 52: 3203
      CrossrefPubMed
    • 10k Senaweera SM, Singh A, Weaver JD. J. Am. Chem. Soc. 2014; 136: 3002
      CrossrefPubMed
    • 10l Lu J, Khetrapal NS, Johnson JA, Zeng XC, Zhang J. J. Am. Chem. Soc. 2016; 138: 15805
      CrossrefPubMed
    • 10m Cybulski MK, Nicholls JE, Lowe JP, Mahon MF, Whittlesey MK. Organometallics 2017; 36: 2308
      Crossref
    • 11a Braun T, Ahijado Salomon M, Altenhöer K, Teltewskoi M, Hinze S. Angew. Chem. Int. Ed. 2009; 48: 1818
      CrossrefPubMed
    • 11b Teltewskoi M, Panetier JA, Macgregor SA, Braun T. Angew. Chem. Int. Ed. 2010; 49: 3947
      CrossrefPubMed
    • 11c Lindup RJ, Marder TB, Perutz RN, Whitwood AC. Chem. Commun. 2007; 3664
      PubMed
    • 11d Liu XW, Echavarren J, Zarate C, Martin R. J. Am. Chem. Soc. 2015; 137: 12470
      CrossrefPubMed
    • 11e Niwa T, Ochiai H, Watanabe Y, Hosoya T. J. Am. Chem. Soc. 2015; 137: 14313
      CrossrefPubMed
    • 11f Kalläne SI, Teltwskoi M, Braun T, Braun B. Organometallics 2015; 34: 1156
      Crossref
    • 11g Zhou J, Kuntze-Fechner MW, Bertermann R, Paul US. D, Berthel JH. J, Friedrich A, Du Z, Marder TB, Radius U. J. Am. Chem. Soc. 2016; 138: 5250
      CrossrefPubMed
    • 11h Tian Y.-M, Guo X.-N, Kuntze-Fechner MW, Krummenacher I, Braunschweig H, Radius U, Steffen A, Marder TB. J. Am. Chem. Soc. 2018; 140: 17612
      CrossrefPubMed

      For Ni-catalyzed arylations, see:
    • 12a Yoshikai N, Mashima H, Nakamura E. J. Am. Chem. Soc. 2005; 127: 17978
      CrossrefPubMed
    • 12b Schaub T, Backes M, Radius U. J. Am. Chem. Soc. 2006; 128: 15964
      CrossrefPubMed
    • 12c Sun AD, Love JA. Org. Lett. 2011; 13: 2750
      CrossrefPubMed
    • 12d Tobisu M, Xu T, Shimasaki T, Chatani N. J. Am. Chem. Soc. 2011; 133: 19505
      CrossrefPubMed
    • 12e Nakamura Y, Yoshikai N, Ilies L, Nakamura E. Org. Lett. 2012; 14: 3316
      CrossrefPubMed
    • 12f Ohashi M, Saijo H, Shibata M, Ogoshi S. Eur. J. Org. Chem. 2013; 443
    • 12g Saijo H, Sakaguchi H, Ohashi M, Ogoshi S. Organometallics 2014; 33: 3669
      Crossref
    • 12h Zhou J, Berthel JH. J, Kuntze-Fechner MW, Friedrich A, Marder TB, Radius U. J. Org. Chem. 2016; 81: 5789
      CrossrefPubMed
    • 12i Zhu F, Wang Z.-X. J. Org. Chem. 2014; 79: 4285
      CrossrefPubMed

      • For Pd-catalyzed arylations, see:
    • 12j Macgregor SA, Roe DC, Marshall WJ, Bloch KM, Bakhmutov VI, Grushin VV. J. Am. Chem. Soc. 2005; 127: 15304
      CrossrefPubMed
    • 12k Cargill MR, Sandford G, Tadeusiak AJ, Yufit DS, Howard JA. K, Kilickiran P, Nelles G. J. Org. Chem. 2010; 75: 5860
      CrossrefPubMed
    • 12l Yu D, Lu L, Shen Q. Org. Lett. 2013; 15: 940
      CrossrefPubMed
    • 12m Ohashi M, Doi R, Ogoshi S. Chem. Eur. J. 2014; 20: 2040
      CrossrefPubMed
    • 12n Luo Z.-J, Zhao H.-Y, Zhang X. Org. Lett. 2018; 20: 2543
      CrossrefPubMed
    • 13a Wang T, Alfonso BJ, Love JA. Org. Lett. 2007; 9: 5629
      CrossrefPubMed
    • 13b Buckley HL, Sun AD, Love JA. Organometallics 2009; 28: 6622
      Crossref
    • 13c Sun AD, Love JA. J. Fluorine Chem. 2010; 131: 1237
      Crossref
    • 13d Sun AD, Leung K, Restivo AD, LaBerge NA, Takasaki H, Love JA. Chem. Eur. J. 2014; 20: 3162
      CrossrefPubMed
    • 13e Yang X, Sun H, Zhang S, Li X. J. Organomet. Chem. 2013; 723: 36
      Crossref
    • 13f Xiao S.-H, Xiong Y, Zhang X.-X, Cao S. Tetrahedron 2014; 70: 4405
      Crossref
  • 14 Guo H, Kong F, Kanno K.-i, He J, Nakajima K, Takahashi T. Organometallics 2006; 25: 2045
    Crossref
    • 15a Iwasaki T, Fukuoka A, Min X, Yokoyama W, Kuniyasu H, Kambe N. Org. Lett. 2016; 18: 4868
      CrossrefPubMed
    • 15b Iwasaki T, Okamoto K, Kuniyasu H, Kambe N. Chem. Lett. 2017; 46: 1504
      Crossref
    • 15c Iwasaki T, Min X, Fukuoka A, Zhu L, Qiu R, Yang T, Ehara M, Sudalai A, Kambe N. J. Org. Chem. 2018; 83: 9267
      CrossrefPubMed
    • 16a Rendler S, Oestreich M. Angew. Chem. Int. Ed. 2007; 46: 498
      CrossrefPubMed
    • 16b Deutsch C, Krause N, Lipshutz BH. Chem. Rev. 2008; 108: 2916
      CrossrefPubMed
    • 16c Fujihara T, Semba K, Terao J, Tsuji Y. Catal. Sci. Technol. 2014; 4: 1699
      Crossref
    • 16d Pirnot MT, Wang Y.-M, Buchwald SL. Angew. Chem. Int. Ed. 2016; 55: 48
      CrossrefPubMed
    • 16e Jordan AJ, Lalic G, Sadighi JP. Chem. Rev. 2016; 116: 8318
      CrossrefPubMed
    • 16f Chen J, Guo Z, Lu Z. Chin. J. Chem. 2018; 36: 1075
      Crossref
    • 16g Liu RY, Buchwald SL. Acc. Chem. Res. 2020; 53: 1229
      CrossrefPubMed
    • 17a Semba K, Ariyama K, Zheng H, Kameyama R, Sakaki S, Nakao Y. Angew. Chem. Int. Ed. 2016; 55: 6275
      CrossrefPubMed
    • 17b Friis SD, Pirnot MT, Buchwald SL. J. Am. Chem. Soc. 2016; 138: 8372
      CrossrefPubMed
    • 17c Friis SD, Pirnot MT, Dupuis LN, Buchwald SL. Angew. Chem. Int. Ed. 2017; 56: 7242
      CrossrefPubMed
    • 17d Armstrong MK, Goodstein MB, Lalic G. J. Am. Chem. Soc. 2018; 140: 10233
      CrossrefPubMed
    • 17e Armstrong MK, Lalic G. J. Am. Chem. Soc. 2019; 141: 6173
      CrossrefPubMed
    • 17f Kortman GD, Hull KL. ACS Catal. 2017; 7: 6220
      Crossref
    • 18a Xu G, Zhao H, Fu B, Cang A, Zhang G, Zhang Q, Xiong T, Zhang Q. Angew. Chem. Int. Ed. 2017; 56: 13130
      CrossrefPubMed
    • 18b Xu G, Fu B, Zhao H, Li Y, Zhang G, Wang Y, Xiong T, Zhang Q. Chem. Sci. 2019; 10: 1802
      CrossrefPubMed
    • 18c Fu B, Yuan X, Li Y, Wang Y, Zhang Q, Xiong T, Zhang Q. Org. Lett. 2019; 21: 3576
      CrossrefPubMed
    • 18d Wang H, Zhang G, Zhang Q, Wang Y, Li Y, Xiong T, Zhang Q. Chem. Commun. 2020; 56: 1819
      CrossrefPubMed
    • 18e Zhang G, Liang Y, Qin T, Xiong T, Liu S, Guan W, Zhang Q. CCS Chem. 2020; 2: 1737
  • 19 Li X, Fu B, Zhang Q, Yuan X, Zhang Q, Xiong T, Zhang Q. Angew. Chem. Int. Ed. 2020; 59: 23056
    CrossrefPubMed