In order to examine the impact of various parameters in oxygen-promoted imine formation, optimization reactions were carried out, utilizing benzyl alcohol and aniline as model system. Selected results are depicted in Table . At first, different bases were investigated, showing good reactivity for strong bases. In this context, quantitative product formation could be observed for KO t Bu (Table , entry 1) at room temperature in toluene. Notably, under the same reaction conditions, only traces of product were formed with KOH. Concerning the solvent, high conversions were detected in toluene and THF. It should be noted that poor reactivity was observed, if the reaction was carried out under argon atmosphere and under UV-irradiation (Table , entries 8 and 9). Interestingly, TEMPO can be used as efficient promotor under oxygen-free conditions (Table , entry 10). Having established the optimal conditions, scope and limitation of the introduced protocol was explored. In this context, anilines, containing electron-donating or -withdrawing groups, were reacted with benzyl alcohol to give excellent yields (Table ). Furthermore, the condensation of substituted benzyl alcohols with anilines was examined (Table , entries 1s-1ah), showing high reactivity for most substrates. The introduced protocol tolerates a wide range of functional groups including halides, (thio)ethers, alkenes, acetals, the nitro-group as well as electron-rich or electron-poor heterocycles. However, a massive drop in reactivity was observed for the reaction of aniline with 1octanol (see Table , entry 1ai).