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This report details the first organocatalytic method for nitrenoid transfer and its application to intermolecular, site-selective C(sp3)-H amination. The method utilizes a trifluoromethyl iminium salt as the catalyst, iminoiodinanes as the nitrogen source, and substrate as the limiting reagent. Activated, benzylic, and aliphatic substrates can all be selectively functionalized in yields up to 87%.
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