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Article Dans Une Revue Chem Année : 2021

Unlocking the Friedel-Crafts arylation of primary aliphatic alcohols and epoxides driven by hexafluoroisopropanol

Résumé

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
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Origine : Publication financée par une institution

Dates et versions

hal-03468221 , version 1 (07-12-2021)

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Paternité - Pas d'utilisation commerciale - Pas de modification

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Shaofei Zhang, Marie Vayer, Florent Noël, Vuk D Vuković, Andrei Golushko, et al.. Unlocking the Friedel-Crafts arylation of primary aliphatic alcohols and epoxides driven by hexafluoroisopropanol. Chem, In press, ⟨10.1016/j.chempr.2021.10.023⟩. ⟨hal-03468221⟩
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