ArticleNature chemistry2026
A pyridoxal radical carboligase and imine reductase photobiocatalytic cascade for stereoselective synthesis of unnatural prolines.
Article in Nature chemistry, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 8 papers.
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Who cites it
8 citing papers in PubMed.
- Photometallobiocatalytic Asymmetric Radical-Mediated Cross-Coupling of Organotrifluoroborate Salts and Pyridotriazoles.Angewandte Chemie (International ed. in English) · 2026Article
- Sustainable Biocatalytic Cascades: A Versatile Tool in the Synthesis of Natural Products With Therapeutic Potential.Chembiochem : a European journal of chemical biology · 2026Review
- Article
- Catalytically Promiscuous PLP-Dependent Aminotransferases Are Biocatalysts for C-C Bond Formation.ACS central science · 2026Article
- Eco-Nanozymology: A Catalytic Paradigm Integrating Energy, Environment, and Ecology.Nano-micro letters · 2026Review
- Integrating microbial cell factory with new-to-nature photobiocatalysis for de novo biosynthesis of D-homotryptophan.Nature communications · 2026Article
- Directed Evolution of Threonine Aldolases for the Photobiocatalytic Synthesis of β-Branched-α-Tetrasubstituted and Other Noncanonical Amino Acids.Journal of the American Chemical Society · 2026Article
- Harnessing Photoenzymatic Systems for Intermolecular C-H Fluorination.Angewandte Chemie (International ed. in English) · 2026Article
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8 authors.
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Abstract
Cooperative photobiocatalysis is a useful strategy for achieving stereoselective intermolecular radical reactions that are not known in either biology or chemistry. The diastereoselective and enantioselective synthesis of cyclic non-canonical amino acids remains challenging using established methods. Here we report a multienzyme photobiocatalytic cascade to stereoselectively prepare polysubstituted unnatural prolines. We engineered an underexploited class of pyridoxal 5'-phosphate aldolases as new-to-nature radical carboligases to catalyse the decarboxylative C-C coupling of aspartic acid, furnishing imine-containing azacyclic non-canonical amino acids. High-throughput screening of metagenomic imine reductases led to the development of diastereoselective biocatalytic reduction and dynamic kinetic asymmetric transformation of cyclic imines, providing optically pure unnatural prolines featuring an elusive 2,5-anti stereochemistry with up to three stereocentres. Beyond its synthetic utility, this study established a new mode of radical pyridoxal enzymology by leveraging open-shell enamine catalysis, opening up avenues for developing new free radical reactions.
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