Harnessing Dual\nReactivity of <i>N</i>‑Chloroamides\nfor Cascade C–H Amidation/Chlorination of Indoles under Cobalt-Catalysis:\nOverriding Hofmann Rearrangement Pathway Leading to Aminocarbonylation

Herein, we have developed a Cp*Co(III)-catalyzed cascade\nC-2 amidation/C-3\nchlorination of indoles by leveraging the dual functionality of <i>N</i>-chloroamides at ambient temperature. This protocol avoids\nthe aminocarbonylation pathway that may result from the C–H\nfunctionalization of isocyanates formed via a potential Hofmann rearrangement\nof <i>N</i>-chloroamides. In fact, this represents the first\nexample of directed C–H amidation using <i>N</i>-chloroamides\nas amidating agent. The control experiment indicated that the C-2\nC–H amidation occurs prior to C-3 chlorination. Additionally,\nchloro functionality has been effectively utilized for the construction\nof C–S and C–N bonds, thereby expanding the molecular\ndiversity of the synthesized compounds.