The concatenation of the Ugi four‐component synthesis and the CAL B‐catalyzed aminolysis of the intermediary formed Ugi methyl ester products furnishes a novel consecutive five‐component reaction for the formation of triamides. This one‐pot process is excellently compatible with metal catalyzed processes, such as copper‐catalyzed alkyne‐azide cycloaddition and Suzuki cross‐coupling or both in a one‐pot fashion. These novel consecutive six‐component syntheses represent a practical tool for synthesizing substrate libraries of complex triamide structures in a diversity‐oriented fashion.
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