Photoredox catalytic access to N,O‐acetals from enamides by means of electron‐poor perylene bisimides

N,O‐acetals are found as structural motif in natural products and are important synthetic precursors for N‐acylimines as building blocks in organic synthesis for C‐C‐bond formation and amines. For the synthesis of N,O‐acetals, an acid‐, base‐ and metal‐free catalytic method is reported applying N,N‐di‐(2,6‐diisopropyl)‐1,7‐dicyano‐perylen‐3,4,9,10‐tetracarboxylic acid imide and N,N‐di‐(2,6‐diisopropyl)‐1,6,7,12‐tetrabromo‐2,5,8,11‐tetracyano‐perylen‐3,4,9,10‐tetracarboxylic acid imide as extremely electron‐deficient photocatalysts. The first perylene bisimide highly selectively photocatalyzes the formation of the N,O‐acetals as products in high yields, and the second and more electron‐deficient perylene bisimide allows these reactions without thiophenol as H‐atom transfer reagent. Calculated electron density maps support this. The reaction scope comprises different substituents at the nitrogen of the enamides and different alcohols as starting material. Dehydroalanines are converted to non‐natural amino acids that shows the usefulness of this method for organic and medicinal chemistry.