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Redox-ligand sustains controlled generation of CF3 radicals by well-defined copper complex
Jérémy Jacquet1, Sébastien Blanchard1, Etienne Derat1
1Institut Parisien de Chimie Moléculaire , UMR CNRS 8232 , Sorbonne Universités UPMC Univ Paris 06 , 4 Place Jussieu, CC 229 , 75252 Paris Cedex 05 , France . Email: marine.desage-el_murr@upmc.fr ;
Abstract:
A well-defined copper complex bearing iminosemiquinone ligands performs single electron reduction of an electrophilic CF3+ source into CF˙3 radicals. This redox behavior is enabled by the ligand which shuttles through two different redox states (iminosemiquinone and iminobenzoquinone) while the copper center is preserved as a Cu(ii). This system was used in the trifluoromethylation of silyl enol ethers, heteroaromatics and in the hydrotrifluoromethylation of alkynes. This is the first example of cooperative redox catalysis for the controlled generation of CF˙3 radicals.
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