Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Photosensitized oxidative addition to gold(i) enables alkynylative cyclization of o-alkylnylphenols with iodoalkynes

Nature Chemistry volume 11, pages 797–805 (2019)Cite this article

Subjects

Abstract

The well-established oxidative addition–reductive elimination pathway is the most followed one in transition metal-catalysed cross-coupling reactions. While readily occurring with a series of transition metals, gold(i) complexes have shown some reluctance to undergo oxidative addition unless special sets of ligands on gold(i), reagents or reaction conditions are used. Here we show that under visible-light irradiation, an iridium photocatalyst triggers—via triplet sensitization—the oxidative addition of an alkynyl iodide onto a vinylgold(i) intermediate to deliver C(sp)2–C(sp) coupling products after reductive elimination. Mechanistic and modelling studies support that an energy-transfer event takes place, rather than a redox pathway. This particular mode of activation in gold homogenous catalysis was applied in several dual catalytic processes. Alkynylbenzofuran derivatives were obtained from o-alkynylphenols and iodoalkynes in the presence of catalytic gold(i) and iridium(iii) complexes under blue light-emitting diode irradiation.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Learn more

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Gold-catalysed additions to alkynes.
Fig. 2: A vinylgold(i) species as a plausible intermediate.
Fig. 3: Potential surface energy of the reaction of 36 with 2a.
Fig. 4: Mechanism proposal.
Fig. 5: Scope of the alkynylation process.

Data availability

Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers 1850903 ( 3aa ) and 1850902 ( 6 ). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the Article and the Supplementary Information, or from the corresponding authors on reasonable request.

References

  1. Dorel, R. & Echavarren, A. M. Gold(I)-catalyzed activation of alkynes for the construction of molecular complexity. Chem. Rev. 115, 9028–9072 (2015).

    Article  CAS  Google Scholar 

  2. Fensterbank, L. & Malacria, M. Molecular complexity from polyunsaturated substrates: the gold catalysis approach. Acc. Chem. Res. 47, 953–965 (2014).

    Article  CAS  Google Scholar 

  3. Harris, R. J. & Widenhoefer, R. A. Gold carbenes, gold-stabilized carbocations, and cationic intermediates relevant to gold-catalysed enyne cycloaddition. Chem. Soc. Rev. 45, 4533–4551 (2016).

    Article  CAS  Google Scholar 

  4. Wang, W., Hammond, G. B. & Xu, B. Ligand effects and ligand design in homogeneous gold(I) catalysis. J. Am. Chem. Soc. 134, 5697–5705 (2012).

    Article  CAS  Google Scholar 

  5. Liu, L.-P. & Hammond, G. Recent advances in the isolation and reactivity of organogold complexes. Chem. Soc. Rev. 41, 3129–3139 (2012).

    Article  CAS  Google Scholar 

  6. Hashmi, A. S. K. et al. Scope and limitations of palladium-catalyzed cross-coupling reactions with organogold compounds. Adv. Synth. Catal. 352, 1307–1314 (2010).

    Article  CAS  Google Scholar 

  7. Garcia-Dominguez, P. & Nevado, C. Au−Pd bimetallic catalysis: the importance of anionic ligands in catalyst speciation. J. Am. Chem. Soc. 138, 3266–3269 (2016).

    Article  CAS  Google Scholar 

  8. Zheng, Z., Wang, Z., Wang, Y. & Zhang, L. Au-catalysed oxidative cyclisation. Chem. Soc. Rev. 45, 4448–4458 (2016).

    Article  CAS  Google Scholar 

  9. Hopkinson, M. N., Tlahuext-Aca, A. & Glorius, F. Merging visible light photoredox and gold catalysis. Acc. Chem. Res. 49, 2261–2272 (2016).

    Article  CAS  Google Scholar 

  10. Sahoo, B., Hopkinson, M. N. & Glorius, F. Combining gold and photoredox catalysis: visible light-mediated oxy- and aminoarylation of alkenes. J. Am. Chem. Soc. 135, 5505–5508 (2013).

    Article  CAS  Google Scholar 

  11. Tlahuext-Aca, A., Hopkinson, M. N., Sahoo, B. & Glorius, F. Dual gold/photoredox-catalyzed C(sp)–H arylation of terminal alkynes with diazonium salts. Chem. Sci 7, 89–93 (2016).

    Article  CAS  Google Scholar 

  12. Shu, X.-Z., Zhang, M., Frei, H. & Toste, F. D. Dual visible light photoredox and gold-catalyzed arylative ring expansion. J. Am. Chem. Soc. 136, 5844–5847 (2014).

    Article  CAS  Google Scholar 

  13. Kim, S., Rojas-Martin, J. & Toste, F. D. Visible light-mediated gold-catalysed carbon(sp2)–carbon(sp) cross-coupling. Chem. Sci. 7, 85–88 (2016).

    Article  CAS  Google Scholar 

  14. Levin, M. D., Kim, S. & Toste, F. D. Photoredox catalysis unlocks single-electron elementary steps in transition metal catalyzed cross-coupling. ACS Cent. Sci. 2, 293–301 (2016).

    Article  CAS  Google Scholar 

  15. Skubi, K. L., Blum, T. R. & Yoon, T. P. Dual catalysis strategies in photochemical synthesis. Chem. Rev. 116, 10035–10074 (2016).

    Article  CAS  Google Scholar 

  16. Twilton, J., Le, C., Zhang, P., Evans, R. W. & MacMillan, D. W. C. The merger of transition metal and photocatalysis. Nat. Rev. Chem 1, 0052 (2017).

    Article  CAS  Google Scholar 

  17. Patil, D. V., Yun, H. & Shin, S. Catalytic cross-coupling of vinyl golds with diazonium salts under photoredox and thermal conditions. Adv. Synth. Catal. 357, 2622–2628 (2015).

    Article  CAS  Google Scholar 

  18. Um, J., Yun, H. & Shin, S. Cross-coupling of Meyer–Schuster intermediates under dual gold–photoredox catalysis. Org. Lett. 18, 484–487 (2016).

    Article  CAS  Google Scholar 

  19. Huang, L., Rudolph, M., Rominger, F. & Hashmi, A. S. K. Photosensitizer-free visible light mediated gold catalyzed 1,2-difunctionalization of alkynes. Angew. Chem. Int. Ed. 55, 4808–4813 (2016).

    Article  CAS  Google Scholar 

  20. Tlahuext-Aca, A., Hopkinson, M. N., Garza-Sanchez, R. A. & Glorius, F. Alkyne difunctionalization by dual gold/photoredox catalysis. Chem. Eur. J 22, 5909–5913 (2016).

    Article  CAS  Google Scholar 

  21. Alcaide, B., Almendros, P., Busto, E. & Luna, A. Domino Meyer–Schuster/arylation reaction of alkynols or alkynyl hydroperoxides with diazonium salts promoted by visible light under dual gold and ruthenium catalysis. Adv. Synth. Catal. 358, 1526–1533 (2016).

    Article  CAS  Google Scholar 

  22. Cornilleau, T., Hermange, P. & Fouquet, E. Gold-catalysed cross-coupling between aryldiazonium salts and arylboronic acids: probing the usefulness of photoredox conditions. Chem. Commun. 52, 10040–10043 (2016).

    Article  CAS  Google Scholar 

  23. Gauchot, V. & Lee, A.-L. Dual gold photoredox C(sp2)-C(sp2) cross couplings – development and mechanistic studies. Chem. Commun. 52, 10163–10166 (2016).

    Article  CAS  Google Scholar 

  24. Gauchot, V., Sutherland, D. R. & Lee, A.-L. Dual gold and photoredox catalysed C–H activation of arenes for aryl–aryl cross couplings. Chem. Sci 8, 2885–2889 (2017).

    Article  CAS  Google Scholar 

  25. Tlahuext-Aca, A., Hopkinson, M. N., Daniliuc, C. G. & Glorius, F. Oxidative addition to gold(I) by photoredox catalysis: straightforward access to diverse (C,N)- cyclometalated gold(III) complexes. Chem. Eur. J 22, 11587–11592 (2016).

    Article  CAS  Google Scholar 

  26. Zhang, Q., Zhang, Z.-Q., Fu, Y. & Yu, H.-Z. Mechanism of the visible light-mediated gold-catalyzed oxyarylation reaction of alkenes. ACS Catal 6, 798–808 (2016).

    Article  CAS  Google Scholar 

  27. Zhou, Q.-Q., Zou, Y.-Q., Lu, L.-Q. & Xiao, W.-J. Visible-light-induced organic photochemical reactions through energy-transfer pathways. Angew. Chem. Int. Ed. 58, 1586–1604 (2019).

    Article  CAS  Google Scholar 

  28. Strieth-Kalthoff, F., James, J. M., Teders, M., Pitzer, L. & Glorius, F. Energy transfer catalysis mediated by visible light: principles, applications, directions. Chem. Soc. Rev. 47, 7190–7202 (2018).

    Article  CAS  Google Scholar 

  29. de Haro, T. & Nevado, C. Gold-Catatalyzed Ethynylation of Arenes. J. Am. Chem. Soc. 132, 1512–1513 (2010).

    Article  Google Scholar 

  30. Hopkinson, M. N., Ross, J. E., Giuffredi, G. T., Gee, A. D. & Gouverneur, V. Gold-catalyzed cascade cyclization−oxidative alkynylation of allenoates. Org. Lett. 12, 4904–4907 (2010).

    Article  CAS  Google Scholar 

  31. Li, Y., Brand, J. P. & Waser, J. Gold-catalyzed regioselective synthesis of 2- and 3-alkynyl furans. Angew. Chem. Int. Ed. 52, 6743–6747 (2013).

    Article  CAS  Google Scholar 

  32. Xia, Z., Khaled, O., Mouriès-Mansuy, V., Ollivier, C. & Fensterbank, L. Dual photoredox/gold catalysis arylative cyclization of o-alkynylphenols with aryldiazonium salts: a flexible synthesis of benzofurans. J. Org. Chem. 81, 7182–7190 (2016).

    Article  CAS  Google Scholar 

  33. Joost, M., Amgoune, A. & Bourissou, D. Reactivity of gold complexes towards elementary organometallic reactions. Angew. Chem. Int. Ed. 54, 15022–15045 (2015).

    Article  CAS  Google Scholar 

  34. Levin, M. D. & Toste, F. D. Gold-catalyzed allylation of aryl boronic acids: accessing cross-coupling reactivity with gold. Angew. Chem. Int. Ed. 53, 6211–6215 (2014).

    Article  CAS  Google Scholar 

  35. Asomoza-Solis, E. O., Rojas-Ocampo, J., Toscano, R. A. & Porcel, S. Arenediazonium salts as electrophiles for the oxidative addition of gold(I). Chem. Commun. 52, 7295–7298 (2016).

    Article  CAS  Google Scholar 

  36. Huang, L., Rominger, F., Rudolph, M. & Hashmi, A. S. K. A general access to organogold(III) complexes by oxidative addition of diazonium salts. Chem. Commun. 52, 6435–6438 (2016).

    Article  CAS  Google Scholar 

  37. Winston, M. S., Wolf, W. J. & Toste, F. D. Photoinitiated oxidative addition of CF3I to gold(I) and facile aryl-CF3 reductive elimination. J. Am. Chem. Soc. 136, 7777–7782 (2014).

    Article  CAS  Google Scholar 

  38. Serra, J., Parella, T. & Ribas, X. Au(III)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis. Chem. Sci. 8, 946–952 (2017).

    Article  CAS  Google Scholar 

  39. Joost, M. et al. Oxidative addition of carbon–carbon bonds to gold. Angew. Chem. Int. Ed. 54, 14512–14516 (2015).

    Google Scholar 

  40. Joost, M. et al. Facile oxidative addition of aryl iodides to gold(I) by ligand design: bending turns on reactivity. J. Am. Chem. Soc. 136, 14654–14657 (2014).

    Article  CAS  Google Scholar 

  41. Zeineddine, A. et al. Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides. Nat. Commun. 8, 565 (2017).

    Article  Google Scholar 

  42. Harper, M. J. et al. Oxidative addition, transmetalation, and reductive elimination at a 2,2-bipyridyl-ligated gold center. J. Am. Chem. Soc. 140, 4440–4445 (2018).

    Article  CAS  Google Scholar 

  43. Martelli, G., Spagnolo, P. & Tiecco, M. Homolytic aromatic substitution by phenylethynyl radicals. J. Chem. Soc. B 0, 1413–1418 (1970).

    Article  CAS  Google Scholar 

  44. Xie, J. et al. A highly efficient gold–catalyzed photoredox α–C(sp3)–H alkynylation of tertiary aliphatic amines with sunlight. Angew. Chem. Int. Ed. 54, 6046–6050 (2015).

    Article  CAS  Google Scholar 

  45. Hashmi, A. S. K., Ramamurthi, T. D. & Rominger, F. On the trapping of vinylgold intermediates. Adv. Synth. Catal. 352, 971–975 (2010).

    Article  CAS  Google Scholar 

  46. Lowry, M. S. et al. Single-layer electroluminescent devices and photoinduced hydrogen production from an ionic iridium(III) complex. Chem. Mater. 17, 5712–5719 (2005).

    Article  CAS  Google Scholar 

  47. Teders, M. et al. The energy-transfer-enabled biocompatible disulfide–ene reaction. Nat. Chem. 10, 981–988 (2018).

    Article  CAS  Google Scholar 

  48. Porter, G. & Wilkinson, F. Energy transfer from the triplet state. Proc. R. Soc. A 264, 1–18 (1961).

    Article  CAS  Google Scholar 

  49. Kaga, A. et al. Degenerative xanthate transfer to olefins under visible-light photocatalysis. Beilstein J. Org. Chem. 14, 3047–3058 (2018).

    Article  CAS  Google Scholar 

  50. Lu, Z. & Yoon, T. P. Visible light photocatalysis of [2+2] styrene cycloadditions by energy transfer. Angew. Chem. Int. Ed. 51, 10329–10332 (2012).

    Article  CAS  Google Scholar 

  51. Welin, E. R., Le, C., Arias-Rotondo, D. M., McCusker, J. K. & MacMillan, D. W. C. Photosensitized energy transfer-mediated organometallic catalysis through electronically excited nickel(II). Science 355, 380–385 (2017).

    Article  CAS  Google Scholar 

  52. Creutz, S. E., Lotito, K. J., Fu, G. C. & Peters, J. C. Photoinduced Ullmann C–N coupling: demonstrating the viability of a radical pathway. Science 338, 647–651 (2012).

    Article  CAS  Google Scholar 

  53. Yoo, W.-J., Tsukamoto, T. & Kobayashi, S. Visible light-mediated Ullmann-type C–N coupling reactions of carbazole derivatives and aryl iodides. Org. Lett. 17, 3640–3642 (2015).

    Article  CAS  Google Scholar 

  54. Hwang, S. J. et al. Trap-free halogen photoelimination from mononuclear Ni(III) complexes. J. Am. Chem. Soc. 137, 6472–6475 (2015).

    Article  CAS  Google Scholar 

  55. Shields, B. J. & Doyle, A. G. Direct C(sp 3)−H cross-coupling enabled by catalytic generation of chlorine radicals. J. Am. Chem. Soc. 138, 12719–12722 (2016).

    Article  CAS  Google Scholar 

  56. Heitz, D. R., Tellis, J. C. & Molander, G. A. Photochemical nickel-catalyzed C–H arylation: synthetic scope and mechanistic investigations. J. Am. Chem. Soc. 138, 12715–12718 (2016).

    Article  CAS  Google Scholar 

  57. Dumele, O., Wu, D., Trapp, N., Goroff, N. & Diederich, F. Halogen bonding of (iodoethynyl)benzene derivatives in solution. Org. Lett. 16, 4722–4725 (2014).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank Sorbonne Université, CNRS and ANR HyperSiLight for funding and the Chinese Scholarship Council (for PhD grants to Z.X. and F.Z.). We are grateful to O. Khaled for HRMS. This work was granted access to the high performance computing (HPC) resources of the HPCaVe Centre at Sorbonne Université and the authors wish to acknowledge support from the ICMG Chemistry Nanobio Platform-PCECIC, Grenoble, for calculations facilities. J. Forté is acknowledged for the X-ray diffraction analyses.

Author information

Authors and Affiliations

  1. Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, Paris, France

    Zhonghua Xia, Vincent Corcé, Fen Zhao, Cédric Przybylski, Yves Gimbert, Héloïse Dossmann, Virginie Mouriès-Mansuy, Cyril Ollivier & Louis Fensterbank

  2. PASTEUR, Département de Chimie, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, Paris, France

    Agathe Espagne, Ludovic Jullien & Thomas Le Saux

  3. Université Grenoble Alpes and CNRS, DCM (UMR 5250), Grenoble, France

    Yves Gimbert

Authors
  1. Zhonghua Xia
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Vincent Corcé
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Fen Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Cédric Przybylski
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Agathe Espagne
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ludovic Jullien
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Thomas Le Saux
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yves Gimbert
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Héloïse Dossmann
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Virginie Mouriès-Mansuy
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Cyril Ollivier
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Louis Fensterbank
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Z.X., V.C. and F.Z. performed the synthetic experiments and undertook all the physicochemical analyses. C.P. conducted the MS analyses. A.E., L.J. and T.L.S. performed and analysed the luminescence and transient absorption experiments. Y.G. and H.D. carried out computational studies and V.M-M., C.O. and L.F. designed the experiments, collated the data and prepared the manuscript.

Corresponding authors

Correspondence to Virginie Mouriès-Mansuy, Cyril Ollivier or Louis Fensterbank.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Experimental procedures (synthesis, optimization, mechanistic and luminescence studies).

benzofurane 3aa.cif

Crystallographic data for compound 3aa. CCDC reference 1850903.

vinylgold 6.cif

Crystallographic data for compound 6. CCDC reference 1850902.

Rights and permissions

Reprints and Permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Xia, Z., Corcé, V., Zhao, F. et al. Photosensitized oxidative addition to gold(i) enables alkynylative cyclization of o-alkylnylphenols with iodoalkynes. Nat. Chem. 11, 797–805 (2019). https://doi.org/10.1038/s41557-019-0295-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41557-019-0295-9

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing