Evidence map›Paper›PMID 31221855›Full record

ArticleScience (New York, N.Y.)2019

Photoexcitation of flavoenzymes enables a stereoselective radical cyclization.

Kyle F Biegasiewicz, Simon J Cooper, Xin Gao, Daniel G Oblinsky, Ji Hye Kim, Samuel E Garfinkle, Leo A Joyce, Braddock A Sandoval, Gregory D Scholes, Todd K Hyster

Open access · bronzeAbstract read
In one paragraph

Article in Science (New York, N.Y.), 2019. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 158 papers.

0numbers the graph read from it
0cells of the map it votes in
158citing papers in PubMed
21.8field-weighted citation impact, top 1% of its field
1 · What the graph read from it

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.

2 · The registry

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.

3 · Its place in the literature

Who cites it

158 citing papers in PubMed, 423 citations in OpenAlex.

  1. Article
  2. Article
  3. Article
  4. Article
  5. Article
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  8. Article
  9. Enzyme-Integrated Hydrogels for Advanced Biological Applications.Polymer science & technology (Washington, D.C.) · 2026
    Review
  10. Article
  11. Article
  12. Harnessing Photoenzymatic Systems for Intermolecular C-H Fluorination.Angewandte Chemie (International ed. in English) · 2026
    Article
  13. Review
  14. Protein engineering: status report.Protein engineering, design & selection : PEDS · 2026
    Review
  15. Article
  16. New-to-Nature Photoenzymatic Catalysis.Methods in molecular biology (Clifton, N.J.) · 2026
    Article
  17. Designing and Engineering Enzymes for New-to-Nature Photobiocatalysis.Methods in molecular biology (Clifton, N.J.) · 2026
    Review
  18. Article
  19. Article
  20. Article

98 more citing papers are in PubMed but not listed here.

4 · The record

Corrections and comments

PubMed lists nothing against this paper. Absence here is not a guarantee, only a check that was made.

5 · Who and what money

Authors and funding

10 authors at 2 institutions in 1 country.

Kyle F Biegasiewicz *Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.ORCID 0000-0003-1905-1919
Simon J Cooper *Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.ORCID 0000-0003-1465-5879
Xin Gao *Department of Chemistry, Princeton University, Princeton, NJ 08544, USA.ORCID 0000-0002-1202-6633
Daniel G OblinskyDepartment of Chemistry, Princeton University, Princeton, NJ 08544, USA.ORCID 0000-0001-7460-8260
Ji Hye KimDepartment of Chemistry, Princeton University, Princeton, NJ 08544, USA.
Samuel E GarfinkleDepartment of Chemistry, Princeton University, Princeton, NJ 08544, USA.ORCID 0000-0001-7729-9299
Leo A JoyceDepartment of Process Research and Development, Merck, Rahway, NJ 07065, USA.
Braddock A SandovalDepartment of Chemistry, Princeton University, Princeton, NJ 08544, USA.
Gregory D ScholesDepartment of Chemistry, Princeton University, Princeton, NJ 08544, USA.
Todd K HysterDepartment of Chemistry, Princeton University, Princeton, NJ 08544, USA. thyster@princeton.edu.ORCID 0000-0003-3560-355X
Princeton University · USMerck & Co., Inc., Rahway, NJ, USA (United States) · US

Funding

X-ray Scattering Technology CoreP30GM133893 · NIGMS · BROOKHAVEN SCIENCE ASSOC-BROOKHAVEN LAB · PI Sean McSweeney · 2019 to 2026
$38.6M
Life Science and Biomedical technology Research center at NSLS-II LSBRP41GM111244 · NIGMS · BROOKHAVEN SCIENCE ASSOC-BROOKHAVEN LAB · PI MCSWEENEY, SEAN · 2014 to 2018
$16.4M
Case Center for Synchrotron BiosciencesP30EB009998 · NIBIB · CASE WESTERN RESERVE UNIVERSITY · PI CHANCE, MARK R · 2009 to 2018
$8.4M
Hyster (Rivas-Souchet) Diversity SupplementR01GM127703 · NIGMS · PRINCETON UNIVERSITY · PI Todd Kurt Hyster · 2018 to 2026
$2.9M
NIBIB NIH HHS P30 EB009998NIGMS NIH HHS P30 GM133893NIGMS NIH HHS P41 GM111244NIGMS NIH HHS R01 GM127703
6 · The paper itself

Abstract

Photoexcitation is a common strategy for initiating radical reactions in chemical synthesis. We found that photoexcitation of flavin-dependent "ene"-reductases changes their catalytic function, enabling these enzymes to promote an asymmetric radical cyclization. This reactivity enables the construction of five-, six-, seven-, and eight-membered lactams with stereochemical preference conferred by the enzyme active site. After formation of a prochiral radical, the enzyme guides the delivery of a hydrogen atom from flavin-a challenging feat for small-molecule chemical reagents. The initial electron transfer occurs through direct excitation of an electron donor-acceptor complex that forms between the substrate and the reduced flavin cofactor within the enzyme active site. Photoexcitation of promiscuous flavoenzymes has thus furnished a previously unknown biocatalytic reaction.

Indexed as

BiocatalysisCyclizationEnzyme ActivationFMN ReductaseLactamsLightStereoisomerismFMN ReductaseLactams

Identifiers

PMID31221855
PMCPMC7028431
OpenAlexW2951766191

What OpenQuestion holds

Textmetadata
LicenceTDM
Read underepoch 390

Registered trials

None linked

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.