ArticleNature chemistry2023
Using enzymes to tame nitrogen-centred radicals for enantioselective hydroamination.
Article in Nature chemistry, 2023. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 47 papers.
What it found
Each row is one number read from the abstract, on the scale the paper reported it, with its interval. Left of the dashed line favours the treatment, right favours the comparator. Under each row is the sentence it came from. New to these charts? A ten-minute tutorial.
The abstract states no effect estimate the extractor could read, or names no intervention and outcome on the map, so this paper lights no cell and moves no belief. It is still indexed, cited and linked below.
The trial behind it
Trials whose registry record cites this paper, or whose number appears in the abstract. A trial that started after this paper was published is citing it as background, not reporting it.
Neither the registry nor the abstract names a trial number. If this is a trial report, that itself is worth knowing.
Who cites it
47 citing papers in PubMed.
- Nitrene generation and transfer for unnatural biosynthesis in living cells.Nature chemistry · 2026Article
- Asymmetric Hydroamination Using Oxidative Radical Initiation in Flavin Enzymes.Journal of the American Chemical Society · 2026Article
- Biocatalytic site- and stereoselective carbonyl desaturation for late-stage functionalization of cyclic ketones.Nature chemistry · 2026Article
- Synthetic Applications of Hydroxamic Acids and Their Derivatives in Organic Chemistry.ACS organic & inorganic Au · 2026Review
- PCA-Based Database Mining Enables the Discovery of Bacterial Carbene Transferases for Stereodivergent Cyclopropanation.Angewandte Chemie (International ed. in English) · 2026Article
- Asymmetric Hydrogen Atom Transfer.ACS catalysis · 2026Review
- Designing and Engineering Enzymes for New-to-Nature Photobiocatalysis.Methods in molecular biology (Clifton, N.J.) · 2026Review
- A pyridoxal radical carboligase and imine reductase photobiocatalytic cascade for stereoselective synthesis of unnatural prolines.Nature chemistry · 2026Article
- Photoenzymatic catalysis enables enantioselective radical dearomative spirocyclization.Nature communications · 2025Article
- Aromatic Coupling Reactions Catalyzed by "ene"-Reductase under Visible Light Irradiation.ACS omega · 2025Article
- Is a Malleable Active Site Loop the Key to High Substrate Promiscuity? Hybrid, Biocatalytic Route to Structurally Diverse Taxoid Side Chains with Remarkable Dual Stereocontrol.Angewandte Chemie (International ed. in English) · 2025Article
- Enantioconvergent benzylic C(spScience (New York, N.Y.) · 2025Article
- Enantioselective Radical Hydrocyanoalkylation of Alkenes via Photoenzymatic Catalysis.JACS Au · 2025Article
- Emergent Mechanisms in Biocatalysis.ACS central science · 2025Review
- Integrating incompatible tandem photobiocatalysis in artificial cells enables metabolic modulation of natural cells.Science advances · 2025Article
- Designing Enzymatic Reactivity with an Expanded Palette.Chembiochem : a European journal of chemical biology · 2025Review
- An efficient lysate-based approach for biosynthesis of the pyrrolobenzodiazepine natural product tilimycin.Journal of biotechnology · 2025Article
- Synergistic Photoenzymatic Anti-Markovnikov Hydroarylation of Olefins via Heteroaryl Radical Intermediates.Journal of the American Chemical Society · 2025Article
- Enantioselective Hydrodifluoroalkylation of Alkenes with Conformationally Tuned Peptidyl Hydrogen Atom Transfer Catalysts.Journal of the American Chemical Society · 2025Article
- Merging of Two Photoredox Cycles with One Perovskite Catalyst Achieving Dual Functionalization: N-Heterocyclization and Site-Selective Bromination of N-Arylamines.The Journal of organic chemistry · 2025Article
Corrections and comments
PubMed lists nothing against this paper. Absence here is not a guarantee, only a check that was made.
Authors and funding
7 authors.
Funding
Abstract
The formation of C-N bonds-of great importance to the pharmaceutical industry-can be facilitated enzymatically using nucleophilic and nitrene transfer mechanisms. However, neither natural nor engineered enzymes are known to generate and control nitrogen-centred radicals, which serve as valuable species for C-N bond formation. Here we use flavin-dependent 'ene'-reductases with an exogenous photoredox catalyst to selectively generate amidyl radicals within the protein active site. These enzymes are engineered through directed evolution to catalyse 5-exo, 6-endo, 7-endo, 8-endo, and intermolecular hydroamination reactions with high levels of enantioselectivity. Mechanistic studies suggest that radical initiation occurs via an enzyme-gated mechanism, where the protein thermodynamically activates the substrate for reduction by the photocatalyst. Molecular dynamics studies indicate that the enzymes bind substrates using non-canonical binding interactions, which may serve as a handle to further manipulate reactivity. This approach demonstrates the versatility of these enzymes for controlling the reactivity of high-energy radical intermediates and highlights the opportunity for synergistic catalyst strategies to unlock previously inaccessible enzymatic functions.
Indexed as
Identifiers
What OpenQuestion holds
Registered trials
Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.