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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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


  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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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.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Gang Li.

Supplementary information

  1. Supplementary Information

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

  2. CIF file for compound 5

    Crystallographic data for compound 5, CCDC reference 1819284

  3. CIF file for compound 6

    Crystallographic data for compound 6, CCDC reference 1819415

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