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Updated: Apr 11, 2026
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Iodoarene-Catalyzed Stereospecific Intramolecular sp(3) C-H Amination: Reaction Development and Mechanistic Insights
Chendan Zhu1, Yong Liang, Xin Hong
1†State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Abstract:
A new strategy is reported for intramolecular sp(3) C-H amination under mild reaction conditions using iodoarene as catalyst and m-CPBA as oxidant. This C-H functionalization involving iodine(III) reagents generated in situ occurs readily at sterically hindered tertiary C-H bonds. DFT (M06-2X) calculations show that the preferred pathway involves an iodonium cation intermediate and proceeds via an energetically concerted transition state, through hydride transfer followed by the spontaneous C-N bond formation. This leads to the experimentally observed amination at a chiral center without loss of stereochemical information.
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