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An efficient Fe(ClO4)3 ⋅ 6H2O‐promoted hetero‐Pictet‐Spengler reaction has been developed, enabling divergent approaches to plenty of structurally diverse polyheterocyclic spirooxindoles and 3,3‐bistryptophol oxindoles from readily available isatins and substituted aromatic heterocyclic derivatives in up to 98% yield. Mechanistic investigation reveals that the perchloric acid generated upon on hydrolysis...
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