Because chiral amines occur widely in natural products and pharmaceuticals, the development of efficient methods for the synthesis of chiral amines continues to be an important issue in organic chemistry. The enantioselective nucleophilic addition to imines is one of the most useful methods for the construction of chiral amines, and a range of chiral acid-catalyzed enantioselective nucleophilic addition reactions with imines have been reported. We have reported chiral phosphoric acid catalyzed nucleophilic addition reactions with imines, such as the Mannich-type reactions and the Friedel-Crafts alkylation reactions (Scheme 1a-i). Although the enantioselective nucleophilic addition to imines through an ionic process has been widely explored, the radical version of the reaction is still limited in spite of its high substituent tolerance because the enantio-control of free radical is not a trivial issue. Ooi and coworkers 8b and Jiang and coworkers have reported the organo-and photocatalytic enantioselective radical addition of imines employing substrates containing a hydrogen bonding acceptor. In order to upgrade the reactivity of imine into a radical reaction, the excited state of iminium ions is useful due to its high oxidation potential. There are several reports of upgrading reactivity of electrophiles or nucloephiles into photooxidants or reductants (Scheme 1b). Melchiorre and coworkers developed an enantioselective β-alkylation of enals via the excitation of iminium ions, wherein the iminium cations behaved as strong photooxidants (E = +2.3 V vs SCE) to generate radical anions. According to this phenomenon, we hypothesize that the protonation of imines by chiral acids will result in a high oxidation potential (Scheme 1c).