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3-Sulfonyl[1,2,3]triazolo[4,5-b]indoles were efficiently prepared via a tandem catalysis process involving intramolecular ligand stabilized CuAAC and Cu-catalyzed C-N coupling. The obtained 3-sulfonyl[1,2,3]triazolo[4,5-b]indoles could be utilized as α-imino rhodium carbene precursors for the construction of a range of valuable indole molecules including pyrrolo[2,3-b]indoles, spirocyclopropyl iminoindoles, 2,3-dihydropyrrolo[2,3-b]indoles, 3,3'-biindoles, and 2,3'-biindoles.
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