Direct Synthesis of α‐Amino Ketones From Aldehydes and Amines via Photocatalytic In Situ Imines Hydroacylation

α‐Amino ketones have essential applications in pharmaceuticals and organic synthesis. The hydroacylation of imines is an attractive approach to access such valuable compounds. However, existing methods for hydroacylation with readily available aldehydes are highly dependent on the prepreparation of imines. Here, we report a photocatalytic protocol for synthesizing α‐amino ketones directly from aldehydes and amines. This one‐pot reaction proceeds smoothly in the presence of the photocatalyst tetrabutylammonium decatungstate (TBADT) and catalytic amounts of HBr. Aldehydes serve as both precursors for in situ imine formation and subsequent acylating agents. Hydrogen atom transfer (HAT) photocatalysis exhibits excellent two‐stage compatibility, allowing the transformation under mild and simple conditions. This strategy avoids the prepreparation and isolation of imines, providing an atom‐ and step‐economical route for the convenient synthesis of α‐amino ketones.