ArticleJournal of the American Chemical Society2016
Dynamically Complex [6+4] and [4+2] Cycloadditions in the Biosynthesis of Spinosyn A.
Article in Journal of the American Chemical Society, 2016. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 37 papers.
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37 citing papers in PubMed.
- Post-transition State Bifurcations in Reactions That Form Pimarenyl Cation Diastereomers─Implications for Terpene Biosynthesis.Journal of the American Chemical Society · 2025Article
- Interplay between Energy and Entropy Mediates Ambimodal Selectivity of Cycloadditions.Journal of chemical theory and computation · 2024Article
- Molecular Dynamics of the Davies Ambimodal C-H Functionalization/Cope Rearrangement Reaction.The Journal of organic chemistry · 2024Article
- Using the Theozyme Model to Study the Dynamical Mechanism of the Post-Transition State Bifurcation Reaction by NgnD Enzyme.Molecules (Basel, Switzerland) · 2024Article
- Predicting Selectivity with a Bifurcating Surface: Inaccurate Model or Inaccurate Statistics of Dynamics?The journal of physical chemistry. A · 2024Article
- The evolutionary origin of naturally occurring intermolecular Diels-Alderases from Morus alba.Nature communications · 2024Article
- Review
- Computational Design of a Tetrapericyclic Cycloaddition and the Nature of Potential Energy Surfaces with Multiple Bifurcations.Journal of the American Chemical Society · 2023Article
- Computational studies of Brønsted acid-catalyzed transannular cycloadditions of cycloalkenone hydrazones.Beilstein journal of organic chemistry · 2023Article
- Mimicry of the proton wire mechanism of enzymes inside a supramolecular capsule enables β-selective O-glycosylations.Nature chemistry · 2022Article
- Collective Synthesis of Illudalane Sesquiterpenes via Cascade Inverse Electron Demand (4 + 2) Cycloadditions of ThiopheneJournal of the American Chemical Society · 2022Article
- Mechanism of the Stereoselective Catalysis of Diels-Alderase PyrE3 Involved in Pyrroindomycin Biosynthesis.Journal of the American Chemical Society · 2022Article
- Stereoelectronic and dynamical effects dictate nitrogen inversion during valence isomerism in benzene imine.Chemical science · 2022Article
- Byproduct formation during the biosynthesis of spinosyn A and evidence for an enzymatic interplay to prevent its formation.Tetrahedron · 2022Article
- Bifurcating reactions: distribution of products from energy distribution in a shared reactive mode.Chemical science · 2021Article
- Discovery and investigation of natural Diels-Alderases.Journal of natural medicines · 2021Review
- Diversity of the reaction mechanisms of SAM-dependent enzymes.Acta pharmaceutica Sinica. B · 2021Review
- Ab Initio Molecular Dynamics Simulations of the SJournal of the American Chemical Society · 2021Article
- Computational Investigation of the Mechanism of Diels-Alderase PyrI4.Journal of the American Chemical Society · 2020Article
- Solvation Dynamics and the Nature of Reaction Barriers and Ion-Pair Intermediates in Carbocation Reactions.Journal of the American Chemical Society · 2020Article
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7 authors.
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Abstract
SpnF, an enzyme involved in the biosynthesis of spinosyn A, catalyzes a transannular Diels-Alder reaction. Quantum mechanical computations and dynamic simulations now show that this cycloaddition is not well described as either a concerted or stepwise process, and dynamical effects influence the identity and timing of bond formation. The transition state for the reaction is ambimodal and leads directly to both the observed Diels-Alder and an unobserved [6+4] cycloadduct. The potential energy surface bifurcates and the cycloadditions occur by dynamically stepwise modes featuring an "entropic intermediate". A rapid Cope rearrangement converts the [6+4] adduct into the observed [4+2] adduct. Control of nonstatistical dynamical effects may serve as another way by which enzymes control reactions.
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