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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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.
Dorel, R. & Echavarren, A. M. Gold(I)-catalyzed activation of alkynes for the construction of molecular complexity. Chem. Rev. 115, 9028–9072 (2015).
Fensterbank, L. & Malacria, M. Molecular complexity from polyunsaturated substrates: the gold catalysis approach. Acc. Chem. Res. 47, 953–965 (2014).
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).
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).
Liu, L.-P. & Hammond, G. Recent advances in the isolation and reactivity of organogold complexes. Chem. Soc. Rev. 41, 3129–3139 (2012).
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).
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).
Zheng, Z., Wang, Z., Wang, Y. & Zhang, L. Au-catalysed oxidative cyclisation. Chem. Soc. Rev. 45, 4448–4458 (2016).
Hopkinson, M. N., Tlahuext-Aca, A. & Glorius, F. Merging visible light photoredox and gold catalysis. Acc. Chem. Res. 49, 2261–2272 (2016).
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).
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).
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).
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).
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).
Skubi, K. L., Blum, T. R. & Yoon, T. P. Dual catalysis strategies in photochemical synthesis. Chem. Rev. 116, 10035–10074 (2016).
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).
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).
Um, J., Yun, H. & Shin, S. Cross-coupling of Meyer–Schuster intermediates under dual gold–photoredox catalysis. Org. Lett. 18, 484–487 (2016).
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).
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).
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).
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).
Gauchot, V. & Lee, A.-L. Dual gold photoredox C(sp2)-C(sp2) cross couplings – development and mechanistic studies. Chem. Commun. 52, 10163–10166 (2016).
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).
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).
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).
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).
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).
de Haro, T. & Nevado, C. Gold-Catatalyzed Ethynylation of Arenes. J. Am. Chem. Soc. 132, 1512–1513 (2010).
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).
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).
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).
Joost, M., Amgoune, A. & Bourissou, D. Reactivity of gold complexes towards elementary organometallic reactions. Angew. Chem. Int. Ed. 54, 15022–15045 (2015).
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).
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).
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).
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).
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).
Joost, M. et al. Oxidative addition of carbon–carbon bonds to gold. Angew. Chem. Int. Ed. 54, 14512–14516 (2015).
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).
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).
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).
Martelli, G., Spagnolo, P. & Tiecco, M. Homolytic aromatic substitution by phenylethynyl radicals. J. Chem. Soc. B 0, 1413–1418 (1970).
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).
Hashmi, A. S. K., Ramamurthi, T. D. & Rominger, F. On the trapping of vinylgold intermediates. Adv. Synth. Catal. 352, 971–975 (2010).
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).
Teders, M. et al. The energy-transfer-enabled biocompatible disulfide–ene reaction. Nat. Chem. 10, 981–988 (2018).
Porter, G. & Wilkinson, F. Energy transfer from the triplet state. Proc. R. Soc. A 264, 1–18 (1961).
Kaga, A. et al. Degenerative xanthate transfer to olefins under visible-light photocatalysis. Beilstein J. Org. Chem. 14, 3047–3058 (2018).
Lu, Z. & Yoon, T. P. Visible light photocatalysis of [2+2] styrene cycloadditions by energy transfer. Angew. Chem. Int. Ed. 51, 10329–10332 (2012).
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).
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).
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).
Hwang, S. J. et al. Trap-free halogen photoelimination from mononuclear Ni(III) complexes. J. Am. Chem. Soc. 137, 6472–6475 (2015).
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).
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).
Dumele, O., Wu, D., Trapp, N., Goroff, N. & Diederich, F. Halogen bonding of (iodoethynyl)benzene derivatives in solution. Org. Lett. 16, 4722–4725 (2014).
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.
The authors declare no competing interests.
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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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