The Concept of Photozymes: Short Peptides with Photoredox Catalytic Activity for Nucleophilic Additions to α‐Phenyl Styrenes

Conventional photoredox catalytic additions of alcohols to olefins require additives, like thiophenol, promote back electron transfer. The concept “photozymes” assumes that forward and backward transfer steps in a cycle are controllable by substrate binding photocatalytically active peptides. Accordingly, we synthesized short tripeptide modified with 1,7-dicyano-perylene-3,4 : 9,10-tetracarboxylic acid bisimide as catalyst. This peptide undergoes an unconventional the radical anion dianion perylene bisimide-peptide intermediates. reactions α-phenyl styrenes substrates remarkably low catalyst loadings (0.5 mol%) give methoxylation products high yields. for catalysis has significant potential other photocatalytic reactions, particular respect enantioselective photocatalysis.