Encouraged by the high reactivity of the developed methodology we performed mechanistic investigations, employing benzyl alcohol and aniline as model substrates for all experimental and computational investigations. At first, the role of KO t Bu was explored. It should be noted that the purity of KO t Bu was carefully analyzed to exclude traces of potentially (catalytically) active impurities. We could reproduce all results with various batches of KO t Bu from different suppliers with purity levels of 98% up to >99.99%. Furthermore, upon addition of 18-crown-6 as potassium scavenger 88% conversion was detected: This suggests that the metal ion is not involved in the ratedetermining step, ruling out an alkali metal MPV-O pathway (cf. computational investigation). Next, we investigated whether this transformation is driven by a radical mechanism. Although the addition of TEMPO did not lead to a drop in reactivity, the reaction pathway clearly involves radicals, since the addition of the typical radical trap 3,4-chromanediol completely suppressed all reactivity. KO t Bu seems to simply act as a base, forming the benzylate salt, which then forms a radical with oxygen from the air (vide infra). In fact, potassium benzylate can be used as starting material, resulting in moderate yield due to high moisture sensitivity of the salt.