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The selective trifluoromethylation of aryl- and vinylboronic acids proceeds smoothly with CF3SO2Na (Langlois reagent) in the presence of copper catalysts and t-BuOOH. Therefore, the method relies both on transition metal catalysis and selective radical reactions. Advantageously, the protocol can be performed at room temperature under an air atmosphere and avoids the issue of poor regioselectivity.