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

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.

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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.

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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

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.

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

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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.

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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

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