Unlocking the Friedel-Crafts arylation of primary aliphatic alcohols and epoxides driven by hexafluoroisopropanol
| Autor: | Andrei Golushko, Florent Noël, Shaofei Zhang, Marie Vayer, Nazanin Rezajooei, Christopher N. Rowley, Vuk D. Vuković, Joseph Moran, David Lebœuf |
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| Přispěvatelé: | Institut de Science et d'ingénierie supramoléculaires (ISIS), Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Department of Chemistry, Memorial University of Newfoundland, St. John's, Canada, Memorial University of Newfoundland [St. John's], Carleton University, univOAK, Archive ouverte, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Memorial University of Newfoundland = Université Memorial de Terre-Neuve [St. John's, Canada] (MUN) |
| Rok vydání: | 2021 |
| Předmět: |
[CHIM.ORGA]Chemical Sciences/Organic chemistry
010405 organic chemistry General Chemical Engineering Biochemistry (medical) [CHIM.CATA] Chemical Sciences/Catalysis Alcohol [CHIM.CATA]Chemical Sciences/Catalysis General Chemistry Alkylation [CHIM.ORGA] Chemical Sciences/Organic chemistry 010402 general chemistry 01 natural sciences Biochemistry 0104 chemical sciences Catalysis chemistry.chemical_compound chemistry Electrophile Materials Chemistry Nucleophilic substitution Environmental Chemistry Organic chemistry SN2 reaction Brønsted–Lowry acid–base theory Friedel–Crafts reaction |
| Zdroj: | Chem Chem, Cell Press, In press, ⟨10.1016/j.chempr.2021.10.023⟩ Chem, In press, ⟨10.1016/j.chempr.2021.10.023⟩ |
| ISSN: | 2451-9294 |
| DOI: | 10.1016/j.chempr.2021.10.023 |
| Popis: | International audience; Alcohols and epoxides are arguably ideal electrophiles for the Friedel-Crafts alkylation, since they are widely available, require no pre-activation, and produce no stoichiometric waste beyond water. However, neither primary aliphatic alcohols nor most classes of terminal epoxides are compatible with existing intermolecular Friedel-Crafts methodologies, and sequential Friedel-Crafts reactions starting from epoxides consequently remain underexplored. Here, we report that these limitations are easily overcome using Brønsted acid catalysis in hexafluoroisopropanol (HFIP) as a solvent. Electron-poor aromatic epoxides and aliphatic epoxides undergo stereospecific arylation to give an alcohol which, depending on the reaction conditions, can partake in a second nucleophilic substitution with a different arene in one pot. Phenyl ethanols react through a phenonium intermediate, whereas simple aliphatic alcohols participate in a rare intermolecular SN2 Friedel-Crafts process, delivering linear products exclusively. This work provides an alternative to metal-catalyzed cross-couplings for accessing important scaffolds, widening the range of applications of the Friedel-Crafts reaction |
| Databáze: | OpenAIRE |
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