Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=C α intermediate on anatase TiO 2 surface
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...
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Published in | Nature communications Vol. 14; no. 1; p. 4479 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
England
02.08.2023
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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 TiO
(TiO
-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 TiO
-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. |
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AbstractList | 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 TiO
(TiO
-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 TiO
-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. |
Author | Liu, Shenglin Fan, Hongjun Zhang, Z Conrad Du, Xinze |
Author_xml | – sequence: 1 givenname: Xinze orcidid: 0000-0003-0822-5557 surname: Du fullname: Du, Xinze organization: University of Chinese Academy of Sciences, Beijing, 100049, China – sequence: 2 givenname: Hongjun orcidid: 0000-0003-3406-6932 surname: Fan fullname: Fan, Hongjun email: fanhj@dicp.ac.cn organization: State Key Laboratory of Molecular Reaction Dynamics, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China. fanhj@dicp.ac.cn – sequence: 3 givenname: Shenglin surname: Liu fullname: Liu, Shenglin organization: State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China – sequence: 4 givenname: Z Conrad surname: Zhang fullname: Zhang, Z Conrad email: zczhang@yahoo.com, zczhang@yahoo.com organization: Changzhou University, Changzhou, 213164, China. zczhang@yahoo.com |
BackLink | https://www.ncbi.nlm.nih.gov/pubmed/37532708$$D View this record in MEDLINE/PubMed |
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Title | Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=C α intermediate on anatase TiO 2 surface |
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