The importance of nitrogen-containing compounds like naturally-occurring primary and secondary metabolites, such as amino acids/proteins, RNA/DNA, or alkaloids, 1 as well as the value of (synthe:cally accessed) N-containing small molecule-based pharmaceu:cally ac:ve ingredients (APIs) cannot be over-es:mated. 2,3 As a consequence, the development of efficient synthesis methods to install amino groups represents one of the most important targets in synthe:c organic chemistry. Numerous approaches to introduce N-containing func:onali:es within exis:ng carbon-skeletons have been reported. Amongst them, those methods that allow for the direct installa:on of a primary unprotected amino group (-NH2) in the a-posi:on of a carbonyl compound are amongst the most appealing but oUen also most challenging ones. In general, a-nitrogena:ons of carbonyl groups can be achieved by a variety of conceptually different strategies. Approaches relying on the use of nucleophilic Nsources can either be carried out via an appropriate carbonyl a-func:onaliza:on (e.g. halogena:on, oxygena:on, or diazota:on) first, followed by addi:on or subs:tu:on with a suited N-nucleophile either in a racemic or more recently also in a stereoselec:ve (enan:ospecific or enan:oselec:ve) manner. Alterna:vely, nucleophilic N-containing reagents have also been successfully engaged for direct a-amina:ons of carbonyl deriva:ves under oxida:ve condi:ons. On the other hand, (stereoselec:ve) a-amina:ons using suited electrophilic N-transfer reagents have also been well-established, i.e. employing asymmetric catalysis. However in these applica:ons usually more complex reagents and/or subsequent func:onal group manipula:ons (e.g. deprotec:ons or reduc:ons) to access a free NH2func:onality are necessary and accordingly direct free NH2-transfer approaches are s:ll difficult. Recently, the groups of Corey, 8a Kür: 8b and Maulide 8c,d contributed significantly to the field by introducing strategies to facilitate the direct (asymmetric) a-NH2-func:onaliza:on of silyl enol ethers using O-(nitrophenyl) hydroxylamines 14 (Corey 8a and Kür: 8b ; Scheme 1A/B) and amides and ketones via a sulfonium [2,3]-sigmatropic rearrangement process (Maulide 8c,d ; Scheme 1C). Over the last years our group became engaged in the development of (asymmetric) heterofunc:onaliza:on reac:ons using simple inorganic heteroatom transfer reagents under oxida:ve condi:ons. Based on the experience gathered therein and the general interest in direct a-NH2-func:onaliza:ons we now started a program exploring the suitability of aqueous ammonia, which is without doubt the cheapest and most readily available NH2-source, for the direct free NH2-a-func:onaliza:on of different enolate precursors under oxida:ve condi:ons. Based on impressive recent progress when using quaternary ammonium halide (phase-transfer) catalysts (Quatsalts, R4N + X -), i.e. ammonium iodides and bromides, under oxida:ve condi:ons, we focused on the use of simple achiral Quatsalts as catalysts for the herein targeted NH3-based oxida:ve a-amina:ons. As outlined in this contribu:on, this is indeed possible by employing inorganic hypochlorites such as Ca(OCl)2 as a simple oxidants in combina:on with aqueous NH3 as the N-source. Overall, this allows for a straighcorward protocol for direct a-NH2-func:onaliza:ons of pronucleophiles like b-ketoesters, malonates and malonitriles as well as oxindoles (Scheme 1D).