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Ligand-enabled site-selectivity in a versatile rhodium(ii)-catalysed aryl C–H carboxylation with CO2

Nature Catalysis volume 1, pages 469–478 (2018)Cite this article

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Abstract

Although carbon dioxide (CO2) is an attractive renewable carbon source, its utilization to produce fine chemicals through the catalytic carboxylation of unactivated carbon–hydrogen (C–H) bonds is still very limited and remains a challenge, largely because CO2 is thermodynamically and kinetically stable. In particular, the generation of (hetero)aromatic carboxylic acids via a transition-metal-catalysed C–H carboxylation of arenes with CO2 is extremely rare. Here we report a ligand-enabled site-selective carboxylation of 2-arylphenols under atmospheric pressure of CO2 through a Rh2(OAc)4-catalysed and chelation-assisted C–H bond activation. Remarkably, the reaction occurs selectively on the less nucleophilic phenyl group with the promotion of a phosphine ligand, which overrides the site selectivity dictated by the well-known Kolbe–Schmitt type reaction. The non-acidic C–H bonds within several important classes of heterocycles were also efficiently carboxylated with this method. A mechanistic investigation revealed complexes of active catalysts and that this reaction proceeds under redox-neutral reaction conditions.

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Fig. 1: Ligand-enabled site-selective C–H carboxylation of 2-arylphenols with CO2.
Fig. 2: Active-catalyst elucidation.
Fig. 3: Mechanistic studies and tentative catalytic cycle.

Change history

  • 29 April 2020

    In the originally published PDF version of this Article, corresponding author information was missing for author Gang Li. This includes an email address in the affiliations section on the first page, and a line instructing readers who to address ‘correspondence and requests for materials’ to, on the final page. These have now been updated.

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Acknowledgements

We gratefully acknowledge the financial support from the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant no. XDB20000000), Natural Science Foundation of Fujian (2017J06007, 2017J05038), NSFC (Grant nos 21702206 and 21402198), the 100 Talents Program of Fujian Province, the National 1000 Youth Talents Program and the State Key Laboratory of Structural Chemistry.

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Author notes

  1. These authors contributed equally to this work: Lei Fu and Shangda Li.

Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (CAS), Fuzhou, Fujian, China

    Lei Fu, Shangda Li, Zhihua Cai, Yongzheng Ding, Xiao-Qing Guo, Li-Peng Zhou, Daqiang Yuan, Qing-Fu Sun & Gang Li

  2. Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, CAS, Fuzhou, Fujian, China

    Gang Li

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Contributions

L.F. and S.L. performed the experiments and developed the reactions. S.L. did the mechanistic studies. Z.C. helped to develop the reaction of 2-pyridinylphenol. Y.D. helped to prepare the substrates. X.-Q.G., D.Y. and Q.-F.S. collected and analysed the X-ray crystallography data. L.-P.Z. collected the high-resolution mass spectra data of the complexes. G.L. designed and supervised the project and wrote the manuscript with feedback from L.F., S.L. and Z.C.

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Correspondence to Gang Li.

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Supplementary information

Supplementary Information

Supplementary Methods; Supplementary Tables 1–7; Supplementary References; Supplementary Figures 1–98

CIF file for compound 5

Crystallographic data for compound 5, CCDC reference 1819284

CIF file for compound 6

Crystallographic data for compound 6, CCDC reference 1819415

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Fu, L., Li, S., Cai, Z. et al. Ligand-enabled site-selectivity in a versatile rhodium(ii)-catalysed aryl C–H carboxylation with CO2. Nat Catal 1, 469–478 (2018). https://doi.org/10.1038/s41929-018-0080-y

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