A new homogeneous bromine(−I/I) redox catalysis is described, which is based on monomeric bromine(I) compounds containing transferable phthalimidato groups. These catalysts enable intermolecular C−H amination reactions at previously unaccessible aliphatic positions and thus enlarge the synthetic potential of direct C−N bond formation, including its application in the synthesis of alkaloid building blocks. This aspect is demonstrated by a new synthetic approach to aspidospermidine. In addition to the development of the catalyst system, the structures of the involved bromine(I) key catalysts were fully elucidated, including by X‐ray analyses.
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