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