Vicinal chloroamines are key components of natural products and pharmaceuticals (e.g., Scheme 1a) and are broadly useful intermediates for chemical synthesis. The value of this motif has driven the development of new methodologies for their preparation, which has been largely dominated by strategies for alkene aminohalogenation. Asymmetric processes are of particularly high value since nucleophilic substitution allows straightforward diversification to a range of new enantioenriched carbons bearing C-heteroatom bonds. Most of these enantioselective methods use transition metal catalysis, with comparatively few examples of organocatalytic processes. To our knowledge, the formation of aryl vicinal chloramines via organocatalytic asymmetric protonation has not been reported. There are only four reports preparing chiral carbons with C-Cl bonds via enantioselective protonation, all of which generate a-chlorocarbonyl products. Of these, only two proceed via asymmetric protonation of a catalytically generated species (Scheme 1b). Rovis employed NHC catalysis for the synthesis of a-chloroacids. Qiao and Jiang used similar starting materials to generate a-chloroketones using dual amine/photoredox catalysis. This latter process represents the only example of an enantioselective protonation of a catalytically generated prochiral chloroenamine. Here we report the development of a new approach for the synthesis of chiral carbons bearing C-Cl bonds via enantioselective protonation of catalytically generated prochiral chloroenamines (Scheme 1c). This process allows simultaneous formation of a new C-N bond and generation of a new Cl-substituted stereogenic centre under simple reaction conditions, providing access to vicinal chloroamines.