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Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids

We describe the carbonylation of a series of mono and dihydroxy derivatives of polyfluorinated alkylbenzenes and benzocycloalkenes with OH groups at benzylic positions using carbon monoxide in the presence of a superacid (TfOH, a TfOH–SbF(5) mixture, or a FSO(3)H–SbF(5) mixture). It was shown that t...

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Autores principales: Wang, Siqi, Zonov, Yaroslav V., Karpov, Victor M., Luzina, Olga A., Mezhenkova, Tatyana V.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9787639/
https://www.ncbi.nlm.nih.gov/pubmed/36557890
http://dx.doi.org/10.3390/molecules27248757
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author Wang, Siqi
Zonov, Yaroslav V.
Karpov, Victor M.
Luzina, Olga A.
Mezhenkova, Tatyana V.
author_facet Wang, Siqi
Zonov, Yaroslav V.
Karpov, Victor M.
Luzina, Olga A.
Mezhenkova, Tatyana V.
author_sort Wang, Siqi
collection PubMed
description We describe the carbonylation of a series of mono and dihydroxy derivatives of polyfluorinated alkylbenzenes and benzocycloalkenes with OH groups at benzylic positions using carbon monoxide in the presence of a superacid (TfOH, a TfOH–SbF(5) mixture, or a FSO(3)H–SbF(5) mixture). It was shown that the superacid-catalyzed addition of CO to various primary and secondary polyfluorinated alcohols and diols gives the corresponding mono- and dicarboxylic acids or lactones. The efficiency of various superacids depending on alcohol structure was evaluated, and FSO(3)H–SbF(5) yielded the best results in most transformations. The addition of CO to secondary 1-arylalkan-1-ols containing vicinal fluorine atoms was found to be accompanied by elimination of HF with the formation of α,β-unsaturated aryl-carboxylic acids. In contrast to primary and secondary alcohols, conversion of tertiary perfluoro-1,1-diarylalkan-1-ols into carbonylation products is not complete, and the resulting carboxylic acids are easily decarboxylated after water treatment of the reaction mixture.
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spelling pubmed-97876392022-12-24 Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids Wang, Siqi Zonov, Yaroslav V. Karpov, Victor M. Luzina, Olga A. Mezhenkova, Tatyana V. Molecules Article We describe the carbonylation of a series of mono and dihydroxy derivatives of polyfluorinated alkylbenzenes and benzocycloalkenes with OH groups at benzylic positions using carbon monoxide in the presence of a superacid (TfOH, a TfOH–SbF(5) mixture, or a FSO(3)H–SbF(5) mixture). It was shown that the superacid-catalyzed addition of CO to various primary and secondary polyfluorinated alcohols and diols gives the corresponding mono- and dicarboxylic acids or lactones. The efficiency of various superacids depending on alcohol structure was evaluated, and FSO(3)H–SbF(5) yielded the best results in most transformations. The addition of CO to secondary 1-arylalkan-1-ols containing vicinal fluorine atoms was found to be accompanied by elimination of HF with the formation of α,β-unsaturated aryl-carboxylic acids. In contrast to primary and secondary alcohols, conversion of tertiary perfluoro-1,1-diarylalkan-1-ols into carbonylation products is not complete, and the resulting carboxylic acids are easily decarboxylated after water treatment of the reaction mixture. MDPI 2022-12-10 /pmc/articles/PMC9787639/ /pubmed/36557890 http://dx.doi.org/10.3390/molecules27248757 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Wang, Siqi
Zonov, Yaroslav V.
Karpov, Victor M.
Luzina, Olga A.
Mezhenkova, Tatyana V.
Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids
title Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids
title_full Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids
title_fullStr Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids
title_full_unstemmed Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids
title_short Carbonylation of Polyfluorinated 1-Arylalkan-1-ols and Diols in Superacids
title_sort carbonylation of polyfluorinated 1-arylalkan-1-ols and diols in superacids
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9787639/
https://www.ncbi.nlm.nih.gov/pubmed/36557890
http://dx.doi.org/10.3390/molecules27248757
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