Abstract
Ni-catalysed functionalization of strong sigma C–O bonds has become an innovative alternative for forging C–C bonds from simple and readily available phenol-derived precursors. However, these methodologies are poorly understood in mechanistic terms. Here we provide mechanistic knowledge about how Ni catalysts enable sp2–sp2 bond formation between aryl esters and arylzinc species by providing reliable access to on-cycle mononuclear oxidative addition species of aryl esters to Ni(0) complexes bearing monodentate phosphines with either κ1- or κ2-O binding modes. While studying the reactivity and decomposition pathways of these complexes, we have unravelled an intriguing dichotomy exerted by Zn(ii) salts that results in parasitic ligand scavenging, oxidation events and NiZn clusters. We provide evidence that coordinating solvents and ligands disrupt these processes, thus offering knowledge for designing more-efficient Ni-catalysed reactions and a useful entry point to unravel the mechanistic intricacies of related processes.
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Data availability
Experimental procedures and characterization data for the catalysts and the synthesized compounds are included in the Supplementary Information. Crystallographic data are available from the Cambridge Crystallographic Data Centre with the following codes: 5a (CCDC 2017448), 5b (CCDC 2017449), 5c (CCDC 2017447), 6a (CCDC 2017442), 8 (CCDC 2017444), 10 (CCDC 2017446), 11 (CCDC 2017445), 12 (CCDC 2017450), 13 (CCDC 2017441), 14 (CCDC 2017443) and 17 (CCDC 2017440). Other data are available from the corresponding author upon request.
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Acknowledgements
We would like to thank the Institut Català d'Investigació Química (ICIQ) and the European Regional Development Fund (FEDER/MCI) (AEI/PGC2018-096839-B-I00) for financial support. C.S.D. thanks the European Union’s Horizon 2020 under the Marie Curie PREBIST grant agreement 754558, and R.J.S. thanks “la Caixa” Foundation (ID 100010434) under agreement LCF/BQ/SO15/52260010 for financial support. We sincerely thank E. Escudero, M. Martinez and J. Benet for X-ray crystallographic data.
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C.S.D. designed and carried out all of the chemical reactions and analysed the data. R.J.S. participated in preliminary experiments. C.S.D. and R.M. conceived and designed the experiments and prepared the manuscript. All authors contributed to discussions, commented and edited the manuscript.
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Supplementary Information
Supplementary Methods, Figs. 1–50 and Tables 1–3.
Supplementary Data
CIF (crystallographic data) of structure 5a.
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CIF (crystallographic data) of structure 5b.
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CIF (crystallographic data) of structure 5c.
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CIF (crystallographic data) of structure 6a.
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CIF (crystallographic data) of structure 8.
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CIF (crystallographic data) of structure 10.
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CIF (crystallographic data) of structure 11.
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CIF (crystallographic data) of structure 12.
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CIF (crystallographic data) of structure 13.
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CIF (crystallographic data) of structure 14.
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CIF (crystallographic data) of structure 17.
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Day, C.S., Somerville, R.J. & Martin, R. Deciphering the dichotomy exerted by Zn(ii) in the catalytic sp2 C–O bond functionalization of aryl esters at the molecular level. Nat Catal 4, 124–133 (2021). https://doi.org/10.1038/s41929-020-00560-3
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DOI: https://doi.org/10.1038/s41929-020-00560-3
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