In the past decade, two basic activation modes (enamine catalysis and iminium catalysis) based on asymmetric secondary amino catalysts have been introduced. Therefore, numerous high quality studies on the aminocatalysis have been carried out to find out a novel catalytic transformation of ketones and aldehydes. Arecent dual catalytic system combining enamine catalysis with metal catalysis produced a new methodology forα-functionalization of aldehydes, named singly occupied molecular orbital catalysis (SOMO catalysis). In the presence of transition metal complexes such as Fe3+, Ce4+ and Cu2+complexes, the enamine undergoes single electron transfer process to render enamine radical, allowing to access unprecedented transformations. However, the use of stochiometric amounts of metal oxidants lead to environmental pollution. Herein, we studied new methodologies to perform SOMO catalysis under environmentally benign conditions (anodic oxidation and photo-oxidation). Moreover, a mild procedure merging iminium/enamine catalysis and metal catalysis to convert allylic alcohols into functionalization of aldehydes was first presented.
