Hypervalent Iodine(III)-Mediated Umpolung Dialkoxylation of N-Substituted Indoles.

Herein, we report dialkoxylation of N-substituted indoles through a hypervalent iodine-mediated umpolung strategy, affording trans -2,3-dimethoxyindolines with up to 95% yield. In addition, C5-selective bromination of 2,3-dialkoxyindoline via NBS-mediated rearomatization was achieved. DFT calculation of the sequence of electrophilic addition and nucleophilic substitution pathway of N-substituted indoles has also been investigated.