I 2 -Cs 2 CO 3 Mediated Intramolecular C2-Amination and Oxidative Rearrangement Cascade of C-3 Phenylthio Indoles: A Route to Synthesize Thiosulfonate-Embedded 2-Iminoindolin-3-ones.

An efficient, transition-metal-free protocol employing I 2 /Cs 2 CO 3 for the synthesis of thiosulfonate containing 2-iminoindolin-3-ones motifs has been developed from C-3 phenylthio indoles. The reaction proceeded through intramolecular cyclization involving C-N bond formation, leading to the formation of indole-fused benzothiazines as a key intermediate. Remarkably, Cs 2 CO 3 played a crucial role in the reaction as an oxygen source, enabling oxidative rearrangement with [1,4]-sulfonyl migration to furnish the final products with the formation of multiple functional groups such as C═O, C═N, and S-SO 2 .