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A detailed mechanistic investigation of the intramolecular dirhodium tetracarboxylate-catalyzed sulfamate ester C–H amination reaction is presented. These studies provide support for the formation of a sulfamate-derived iminoiodinane, which reacts rapidly with the rhodium catalyst to generate a nitrenoid-type oxidant. Reactivity patterns, Hammett analysis, kinetic isotope measurement, and a cyclopropane...
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