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Deciphering the dichotomy exerted by Zn(ii) in the catalytic sp2 C–O bond functionalization of aryl esters at the molecular level

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 sp2sp2 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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Fig. 1: Catalytic functionalization of aryl sp2 C–O bonds.
Fig. 2: Synthesis of mononuclear and dinuclear oxidative addition species of aryl esters to Ni(0) supported by monodentate ligands.
Fig. 3: Synthesis of Ni(i) carboxylate complexes.
Fig. 4: Uncovering the molecular interaction of Ni(0) and Zn(ii).
Fig. 5: Elucidating the effect of ZnCl2 on well-defined Ni(i) and Ni(ii) complexes.
Fig. 6: Transmetalation reactions with organozinc species.
Fig. 7: Understanding the intricacies of Ni-catalysed arylation of aryl esters mediated by Zn.

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.

Corresponding author

Correspondence to Ruben Martin.

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Supplementary information

Supplementary Information

Supplementary Methods, Figs. 1–50 and Tables 1–3.

Supplementary Data

CIF (crystallographic data) of structure 5a.

Supplementary Data

CIF (crystallographic data) of structure 5b.

Supplementary Data

CIF (crystallographic data) of structure 5c.

Supplementary Data

CIF (crystallographic data) of structure 6a.

Supplementary Data

CIF (crystallographic data) of structure 8.

Supplementary Data

CIF (crystallographic data) of structure 10.

Supplementary Data

CIF (crystallographic data) of structure 11.

Supplementary Data

CIF (crystallographic data) of structure 12.

Supplementary Data

CIF (crystallographic data) of structure 13.

Supplementary Data

CIF (crystallographic data) of structure 14.

Supplementary Data

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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