In this work, for the first time, laccase (metalloenzyme)/3,5‐di‐tert‐butylcatechol (DTBC) as a new class of bioinspired quinone‐based cooperative catalytic oxidation system and laccase/2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) catalyst system were used for the aerobic oxidative synthesis of 2‐substituted quinazolines through cascade reaction of structurally divers aldehydes with 2‐aminobenzylamine. The products were obtained in good to high yields in phosphate buffer (0.1 m, 12.5 mL, pH = 4.5) and acetonitrile (4 vol.‐%) mixture as solvent at 45 °C. Other N‐heterocycles are also successfully oxidized to their aromatic counterparts.

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The Front Cover shows that the biomimetic aerobic oxidative dehydrogenation of nitrogen heterocycles proceeds via intramolecular cooperation between a laccase, as a multi‐copper oxidase, and 3,5‐di‐tert‐butylcatechol (DTBC) or 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO), as an organic co‐catalyst, by means of a low‐activation‐energy process in a green solvent. Molecular oxygen cannot directly oxidize nitrogen heterocycles under mild conditions, therefore, appropriate redox compounds (similar to puzzle pieces) must be employed as a bridge (mediator) between molecular oxygen and the substrate. More information can be found in the https://doi.org/10.1002/ejoc.201800466