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Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=Cα intermediate on anatase TiO2 surface

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  • Xinze Du

    (Chinese Academy of Sciences
    University of Chinese Academy of Sciences)

  • Hongjun Fan

    (Chinese Academy of Sciences)

  • Shenglin Liu

    (Chinese Academy of Sciences)

  • Z. Conrad Zhang

    (Chinese Academy of Sciences
    Changzhou University)

Abstract

C−C bond forming reaction by alkylation of aryl rings is a main pillar of chemistry in the production of broad portfolios of chemical products. The dominant mechanism proceeds via electrophilic substitution of secondary and tertiary carbocations over acid catalysts, forming multiple aryl alkylation products non-selectively through all secondary and tertiary carbons in the alkyl chains but producing little α-C alkylation products because primary carbocations are poorly stable. Herein, we report that anatase TiO2 (TiO2-A) catalyzes nucleophilic α-C alkylation of phenols with alcohols in high selectivity to simply linear alkylphenols. Experimental and computational studies reveal the formation of Ti=C− bond with the α-carbon of the alkyl group at oxygen vacancies of the TiO2-A surface. The subsequent α-C alkylation by selective substitution of phenol ortho-C−H bond is verified by deuterium exchanged substrate and DFT calculations.

Suggested Citation

  • Xinze Du & Hongjun Fan & Shenglin Liu & Z. Conrad Zhang, 2023. "Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=Cα intermediate on anatase TiO2 surface," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-40101-7
    DOI: 10.1038/s41467-023-40101-7
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