Carbon-carbon bond cleavage for Cu-mediated aromatic trifluoromethylations and pentafluoroethylations.

Tsuyuka Sugiishi,Kohsuke Aikawa,Koichi Mikami,Hideki Amii

doi:10.3762/bjoc.11.286

Tsuyuka Sugiishi, Kohsuke Aikawa + Show 2 more

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https://doi.org/10.3762/bjoc.11.286

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Abstract

This short review highlights the copper-mediated fluoroalkylation using perfluoroalkylated carboxylic acid derivatives. Carbon–carbon bond cleavage of perfluoroalkylated carboxylic acid derivatives takes place in fluoroalkylation reactions at high temperature (150–200 °C) or under basic conditions to generate fluoroalkyl anion sources for the formation of fluoroalkylcopper species. The fluoroalkylation reactions, which proceed through decarboxylation or tetrahedral intermediates, are useful protocols for the synthesis of fluoroalkylated aromatics.

Highlights

Organofluorine compounds attract attention because of their applicability in various fields, such as medicine, agrochemical and material science
The use of (N-heterocyclic carbene)copper-trifluoroacetates prepared from trifluoroacetic acid (TFA) was investigated in the decarboxylative trifluoromethylation of aryl halides [37] (Scheme 4)
The perfluoroalkylation reactions mentioned above require a stoichiometric amount of copper reagent, whereas it was found that the addition of silver salts is effective for the copper-mediated trifluoromethylation of aryl iodides [38] (Scheme 5)

Summary

Introduction

Organofluorine compounds attract attention because of their applicability in various fields, such as medicine, agrochemical and material science. In the presence of CuI, CF3CO2Na undergoes trifluoromethylation with aryl halides via decarboxylation [33,34] (Scheme 1). Vicic and co-workers explored the direct generation of CF3Cu from CF3CO2Cu. The use of (N-heterocyclic carbene)copper-trifluoroacetates prepared from trifluoroacetic acid (TFA) was investigated in the decarboxylative trifluoromethylation of aryl halides [37] (Scheme 4). The perfluoroalkylation reactions mentioned above require a stoichiometric amount of copper reagent, whereas it was found that the addition of silver salts is effective for the copper-mediated trifluoromethylation of aryl iodides [38] (Scheme 5).

Results

Conclusion