Skip to main content
SpringerLink
Log in

Sunlight decatungstate photoinduced trifluoromethylations of (hetero)aromatics and electron-poor olefins

  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

Tetrabutylammonium decatungstate has been exploited to photoinduce the trifluoromethylation of (hetero)aromatics and electron-poor olefins. The process made use of the cheap Langlois’ reagent (CF3SO2Na) and occurred under sunlight irradiation in an acetonitrile/water mixture. The trifluoromethylation of (hetero)aromatics required the use of potassium persulfate as an additive and the mono- or bis-trifluoromethylated adducts were obtained, depending on the actual reaction conditions and the chosen substrate.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Fluorine in Pharmaceutical and Medicinal Chemistry. From Biophysical Aspects to Clinical Applications, ed. V. Gouverneur and K. Müller, ICP, Oxford, 2012.

    Google Scholar 

  2. J.-A. Ma, and D. Cahard, Strategies for nucleophilic, electrophilic, and radical trifluoromethylations, J. Fluorine Chem., 2007, 128, 975–996.

    Article  CAS  Google Scholar 

  3. N. Shibata, A. Matsnev, and D. Cahard, Shelf-stable electrophilic trifluoromethylating reagents: A brief historical perspective, Beilstein J. Org. Chem., 2010, 6, 65.

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  4. Y. Ji, T. Brueckl, R. D. Baxter, Y. Fujiwara, I. B. Seiple, S. Su, D. G. Blackmond, and P. S. Baran, Innate C-H trifluoromethylation of heterocycles, Proc. Natl. Acad. Sci. U. S. A., 2011, 108, 14411–14415.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. A. Studer, A “Renaissance” in Radical Trifluoromethylation, Angew. Chem., Int. Ed., 2012, 51, 8950–8958.

    Article  CAS  Google Scholar 

  6. S. Barata-Vallejo, S. M. Bonesi, and A. Postigo, Photocatalytic fluoroalkylation reactions of organic compounds, Org. Biomol. Chem., 2015, 13, 11153–11183.

    Article  CAS  PubMed  Google Scholar 

  7. S. Barata-Vallejo, S. M. Bonesi, and A. Postigo, Perfluoroalkylation reactions of (hetero)arenes, RSC Adv., 2015, 5, 62498–62518.

    Article  CAS  Google Scholar 

  8. C. Alonso, E. de Martínez Marigorta, G. Rubiales, and F. Palacios, Carbon Trifluoromethylation Reactions of Hydrocarbon Derivatives and Heteroarenes, Chem. Rev., 2015, 115, 1847–1935.

    Article  CAS  PubMed  Google Scholar 

  9. T. Chatterjee, N. Iqbal, Y. You, and E. J. Cho, Controlled Fluoroalkylation Reactions by Visible-Light Photoredox Catalysis, Acc. Chem. Res., 2016, 49, 2284–2294.

    Article  CAS  PubMed  Google Scholar 

  10. T. Koike, and M. Akita, Fine Design of Photoredox Systems for Catalytic Fluoromethylation of Carbon-Carbon Multiple Bonds, Acc. Chem. Res., 2016, 49, 1937–1945.

    Article  CAS  PubMed  Google Scholar 

  11. X. Pan, H. Xia, and J. Wu, Recent advances in photoinduced trifluoromethylation and difluoroalkylation, Org. Chem. Front., 2016, 3, 1163–1185.

    Article  CAS  Google Scholar 

  12. D. Ravelli, S. Protti, and M. Fagnoni, Carbon-Carbon Bond Forming Reactions via Photogenerated Intermediates, Chem. Rev., 2016, 116, 9850–9913.

    Article  CAS  PubMed  Google Scholar 

  13. X.-J. Tang, and W. R. Dolbier Jr., Efficient Cu-catalyzed Atom Transfer Radical Addition Reactions of Fluoroalkylsulfonyl Chlorides with Electron-deficient Alkenes Induced by Visible Light, Angew. Chem., Int. Ed., 2015, 54, 4246–4249.

    Article  CAS  Google Scholar 

  14. Q. Lefebvre, N. Hoffmann, and M. Rueping, Photoorganocatalysed and visible light photoredox catalysed trifluoromethylation of olefins and (hetero)aromatics in batch and continuous flow, Chem. Commun., 2016, 52, 2493–2496.

    Article  CAS  Google Scholar 

  15. W. J. Choi, S. Choi, K. Ohkubo, S. Fukuzumi, E. J. Cho, and Y. You, Mechanisms and applications of cyclometalated Pt(ii) complexes in photoredox catalytic trifluoromethylation, Chem. Sci., 2015, 6, 1454–1464.

    Article  CAS  PubMed  Google Scholar 

  16. D. Cantillo, O. de Frutos, J. A. Rincón, C. Mateos, and C. O. Kappe, Continuous Flow α-Trifluoromethylation of Ketones by Metal-Free Visible Light Photoredox Catalysis, Org. Lett., 2014, 16, 896–899.

    Article  CAS  PubMed  Google Scholar 

  17. Y. Yasu, T. Koike, and M. Akita, Three-component Oxytrifluoromethylation of Alkenes: Highly Efficient and Regioselective Difunctionalization of C=C Bonds Mediated by Photoredox Catalysts, Angew. Chem., Int. Ed., 2012, 51, 9567–9571.

    Article  CAS  Google Scholar 

  18. G. Dagousset, A. Carboni, E. Magnier, and G. Masson, Photoredox-Induced Three-Component Azido- and Aminotrifluoromethylation of Alkenes, Org. Lett., 2014, 16, 4340–4343.

    Article  CAS  PubMed  Google Scholar 

  19. Q.-Y. Lin, X.-H. Xu, and F.-L. Qing, Chemo-, Regio-, and Stereoselective Trifluoromethylation of Styrenes via Visible Light-Driven Single-Electron Transfer (SET) and Triplet-Triplet Energy Transfer (TTET) Processes, J. Org. Chem., 2014, 79, 10434–10446.

    Article  CAS  PubMed  Google Scholar 

  20. N. Iqbal, J. Jung, S. Park, and E. Jin Cho, Controlled Trifluoromethylation Reactions of Alkynes through Visible-Light Photoredox Catalysis, Angew. Chem., Int. Ed., 2014, 53, 539–542.

    Article  CAS  Google Scholar 

  21. R. Tomita, T. Koike, and M. Akita, Photoredox-Catalyzed Stereoselective Conversion of Alkynes into Tetrasubstituted Trifluoromethylated Alkenes, Angew. Chem., Int. Ed., 2015, 54, 12923–12927.

    Article  CAS  Google Scholar 

  22. L. Li, X. Mu, W. Liu, Y. Wang, Z. Mi, and C.-J. Li, Simple and Clean Photoinduced Aromatic Trifluoromethylation Reaction, J. Am. Chem. Soc., 2016, 138, 5809–5812.

    Article  CAS  PubMed  Google Scholar 

  23. D. A. Nagib, and D. W. C. MacMillan, Trifluoromethylation of arenes and heteroarenes by means of photoredox catalysis, Nature., 2011, 480, 224–228.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  24. N. J. W. Straathof, H. P. L. Gemoets, X. Wang, J. C. Schouten, V. Hessel, and T. Noël, Rapid Trifluoromethylation and Perfluoroalkylation of Five-Membered Heterocycles by Photoredox Catalysis in Continuous Flow, ChemSusChem., 2014, 7, 1612–1617.

    Article  CAS  PubMed  Google Scholar 

  25. J. Xie, X. Yuan, A. Abdukader, C. Zhu, and J. Ma, Visible-Light-Promoted Radical C–H Trifluoromethylation of Free Anilines, Org. Lett., 2014, 16, 1768–1771.

    Article  CAS  PubMed  Google Scholar 

  26. B. R. Langlois, E. Laurent, and N. Roidot, “Pseudo-cationic” trifluoromethylation of enol esters with sodium trifluoromethanesulfinate, Tetrahedron Lett., 1992, 33, 1291–1294.

    Article  CAS  Google Scholar 

  27. B. R. Langlois, E. Laurent, and N. Roidot, Trifluoromethylation of aromatic compounds with sodium trifluoromethanesulfinate under oxidative conditions, Tetrahedron Lett., 1991, 32, 7525–7258.

    Article  CAS  Google Scholar 

  28. D. J. Wilger, N. J. Gesmundo, and D. A. Nicewicz, Catalytic hydrotrifluoromethylation of styrenes and unactivated aliphatic alkenes via an organic photoredox system, Chem. Sci., 2013, 4, 3160–3165.

    Article  CAS  Google Scholar 

  29. L. Cui, Y. Matusaki, N. Tada, T. Miura, B. Uno, and A. Itoh, Metal-Free Direct C−H Perfluoroalkylation of Arenes and Heteroarenes Using a Photoredox Organocatalyst, Adv. Synth. Catal., 2013, 355, 2203–2207.

    Article  CAS  Google Scholar 

  30. B. Li, D. Fan, C. Yang, and W. Xia, UV light-mediated difunctionalization of alkenes with CF3SO2Na: synthesis of trifluoromethyl phenanthrene and anthrone derivatives, Org. Biomol. Chem., 2016, 14, 5293–5297.

    Article  CAS  PubMed  Google Scholar 

  31. L. Zhu, L.-S. Wang, B. Li, B. Fu, C.-P. Zhang, and W. Li, Operationally simple hydrotrifluoromethylation of alkenes with sodium triflinate enabled by Ir photoredox catalysis, Chem. Commun., 2016, 52, 6371–6374.

    Article  CAS  Google Scholar 

  32. X.-L. Yu, J.-R. Chen, D.-Z. Chen, and W.-J. Xiao, Visible-light-induced photocatalytic azotrifluoromethylation of alkenes with aryldiazonium salts and sodium triflinate, Chem. Commun., 2016, 52, 8275–8278.

    Article  CAS  Google Scholar 

  33. H.-T. Qin, S.-W. Wu, J.-L. Liu, and F. Liu, Photoredox-catalysed redox-neutral trifluoromethylation of vinyl azides for the synthesis of α-trifluoromethylated ketones, Chem. Commun., 2017, 53, 1696–1699.

    Article  CAS  Google Scholar 

  34. Q. Lefebvre, Toward Sustainable Trifluoromethylation Reactions: Sodium Triflinate under the Spotlight, Synlett, 2017, 19–23.

    Google Scholar 

  35. J.-B. Tommasino, A. Brondex, M. Médebielle, M. Thomalla, B. R. Langlois, and T. Billard, Trifluoromethylation Reactions with Potassium Trifluoromethanesulfinate under Electrochemical Oxidation, Synlett, 2002, 1697–1699.

    Google Scholar 

  36. D. Ravelli, S. Protti, and M. Fagnoni, Decatungstate Anion for Photocatalyzed “Window Ledge” Reactions, Acc. Chem. Res., 2016, 49, 2232–2242. and references therein

    Article  CAS  PubMed  Google Scholar 

  37. I. N. Lykakis, E. Evgenidou, and M. Orfanopoulos, Photo-catalysis and Polyoxo-anion Decatungstate in Organic Chemistry: A Manifold Concept for Green Chemistry, Curr. Org. Chem., 2012, 16, 2400–2414.

    Article  CAS  Google Scholar 

  38. M. D. Tzirakis, I. N. Lykakis, and M. Orfanopoulos, Decatungstate as an efficient photocatalyst in organic chemistry, Chem. Soc. Rev., 2009, 38, 2609–2621.

    Article  CAS  PubMed  Google Scholar 

  39. C. L. Hill, Introduction of Functionality into Unactivated Carbon-Hydrogen Bonds. Catalytic Generation and Nonconventional Utilization of Organic Radicals, Synlett, 1995, 127–132.

    Google Scholar 

  40. T. S. Symeonidis, I. Tamiolakis, G. S. Armatas, and I. N. Lykakis, Green photocatalytic organic transformations by polyoxometalates vs. mesoporous TiO2 nanoparticles: selective aerobic oxidation of alcohols, Photochem. Photobiol. Sci., 2015, 14, 563–568.

    Article  CAS  PubMed  Google Scholar 

  41. I. Texier, J. A. Delaire, and C. Giannotti, Reactivity of the charge transfer excited state of sodium decatungstate at the nanosecond time scale, Phys. Chem. Chem. Phys., 2000, 2, 1205–1212.

    Article  CAS  Google Scholar 

  42. L. Capaldo, L. Buzzetti, D. Merli, M. Fagnoni, and D. Ravelli, Smooth Photocatalyzed Benzylation of Electrophilic Olefins via Decarboxylation of Arylacetic Acids, J. Org. Chem., 2016, 81, 7102–7109.

    Article  CAS  PubMed  Google Scholar 

  43. S. Montanaro, D. Ravelli, D. Merli, M. Fagnoni, and A. Albini, Decatungstate As Photoredox Catalyst: Benzylation of Electron-Poor Olefins, Org. Lett., 2012, 14, 4218–4221.

    Article  CAS  PubMed  Google Scholar 

  44. V. De Waele, O. Poizat, M. Fagnoni, A. Bagno, and D. Ravelli, Unraveling the Key Features of the Reactive State of Decatungstate Anion in Hydrogen Atom Transfer (HAT) Photocatalysis, ACS Catal., 2016, 6, 7174–7182.

    Article  CAS  Google Scholar 

  45. M. C. Quattrini, S. Fujii, K. Yamada, T. Fukuyama, D. Ravelli, M. Fagnoni, and I. Ryu, Versatile cross-dehydrogenative coupling of heteroaromatics and hydrogen donors via decatungstate photocatalysis, Chem. Commun., 2017, 53, 2335–2338.

    Article  CAS  Google Scholar 

  46. W. Wei, J. Wen, D. Yang, X. Liu, M. Guo, R. Dong, and H. Wang, Metal-Free Direct Trifluoromethylation of Activated Alkenes with Langlois’ Reagent Leading to CF3-Containing Oxindoles, J. Org. Chem., 2014, 79, 4225–4230.

    Article  CAS  PubMed  Google Scholar 

  47. D. Wang, G.-J. Deng, S. Chen, and H. Gong, Catalyst-free direct C–H trifluoromethylation of arenes in water–acetonitrile, Green Chem., 2016, 18, 5967–5970.

    Article  CAS  Google Scholar 

  48. I. Ryu, A. Tani, T. Fukuyama, D. Ravelli, S. Montanaro, and M. Fagnoni, Efficient C-H/C-N and C-H/C-CO-N Conversion via Decatungstate-Photoinduced Alkylation of Diisopropyl Azodicarboxylate, Org. Lett., 2013, 15, 2554–2557.

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgments

We thank Luca Capaldo and Edoardo Torti (University of Pavia) for preliminary experiments. D. R. thanks the MIUR for financial support (SIR Project “Organic Synthesis via Visible Light Photocatalytic Hydrogen Transfer”; Code: RBSI145Y9R).

Author information

Authors and Affiliations

  1. PhotoGreen Lab, Department of Chemistry, University of Pavia, Viale Taramelli 12, 27100, Pavia, Italy

    Sara Corsico, Maurizio Fagnoni & Davide Ravelli

Authors
  1. Sara Corsico
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Maurizio Fagnoni
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Davide Ravelli
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Davide Ravelli.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Corsico, S., Fagnoni, M. & Ravelli, D. Sunlight decatungstate photoinduced trifluoromethylations of (hetero)aromatics and electron-poor olefins. Photochem Photobiol Sci 16, 1375–1380 (2017). https://doi.org/10.1039/c7pp00179g

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c7pp00179g

Search

Navigation