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A cobalt porphyrin‐catalyzed chlorotrifluoromethylation reaction of olefins is described. The use of CF3SO2Cl as the CF3 radical source and a cobalt catalyst enabled the selective addition of CF3 radicals under thermal conditions. Various functional groups such as esters and Ar–X moieties, which can be reactive with low valent transition metal catalysts, were well‐tolerated in this catalytic process...
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