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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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Autores principales: Du, Xinze, Fan, Hongjun, Liu, Shenglin, Zhang, Z. Conrad
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10397351/
https://www.ncbi.nlm.nih.gov/pubmed/37532708
http://dx.doi.org/10.1038/s41467-023-40101-7
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author Du, Xinze
Fan, Hongjun
Liu, Shenglin
Zhang, Z. Conrad
author_facet Du, Xinze
Fan, Hongjun
Liu, Shenglin
Zhang, Z. Conrad
author_sort Du, Xinze
collection PubMed
description 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(2) (TiO(2)-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(2)-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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spelling pubmed-103973512023-08-04 Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=C(α) intermediate on anatase TiO(2) surface Du, Xinze Fan, Hongjun Liu, Shenglin Zhang, Z. Conrad Nat Commun Article 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(2) (TiO(2)-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(2)-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. Nature Publishing Group UK 2023-08-02 /pmc/articles/PMC10397351/ /pubmed/37532708 http://dx.doi.org/10.1038/s41467-023-40101-7 Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Du, Xinze
Fan, Hongjun
Liu, Shenglin
Zhang, Z. Conrad
Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=C(α) intermediate on anatase TiO(2) surface
title Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=C(α) intermediate on anatase TiO(2) surface
title_full Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=C(α) intermediate on anatase TiO(2) surface
title_fullStr Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=C(α) intermediate on anatase TiO(2) surface
title_full_unstemmed Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=C(α) intermediate on anatase TiO(2) surface
title_short Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=C(α) intermediate on anatase TiO(2) surface
title_sort selective nucleophilic α-c alkylation of phenols with alcohols via ti=c(α) intermediate on anatase tio(2) surface
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10397351/
https://www.ncbi.nlm.nih.gov/pubmed/37532708
http://dx.doi.org/10.1038/s41467-023-40101-7
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