Indole Editing Enabled by HFIP‐Mediated Ring‐Switch Reactions of 3‐Amino‐2‐Hydroxyindolines

This work reports the novel reactivity of hemiaminal as a precursor for indole editing at the multi‐site. The HFIP‐promoted indole editing of indoline hemiaminals affords 2‐arylindoles through a ring‐switch sequence. The key to success of this transformation is to use a cyclic hemiaminal as an α‐amino aldehyde surrogate under transient tautomeric control. This transformation features mild reaction conditions and good yields with broad functional group tolerance. The utility of this transformation is presented through the one‐pot protocol and the synthesis of isocryptolepine. Indole multi‐site editing!! Unprecedented indole multi‐site editing was accomplished by a unique ring‐switch reaction of hemiaminals.