Enantioselective C(<i>sp</i>³)–C(<i>sp</i>³) bond formation by synergistic thiamine-dependent radical biocatalysis and photoredox catalysis

Abstract Radical C(sp3)–C(sp3) bond formation has emerged as a promising strategy for constructing molecules rich in C(sp3)–stereocentres. However, achieving chemo- and enantioselective recombination of two prochiral alkyl radicals remains a substantial challenge. Here we synergistically repurpose a thiamine-dependent benzoylformate decarboxylase (PpBFD) with a photoinduced radical process, unlocking unnatural photobiocatalytic C(sp3)–C(sp3) bond formation. This system converts simple cinnamyl..