ArticleNature chemistry2018
Labelling and determination of the energy in reactive intermediates in solution enabled by energy-dependent reaction selectivity.
Article in Nature chemistry, 2018. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 15 papers.
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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.
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Who cites it
15 citing papers in PubMed.
- Evolution of manganese low-energy photoredox catalysis from high-energy visible light photocatalysis.Nature communications · 2026Article
- Probing the Oxidative Addition Transition State in Nickel Metallaphotoredox Catalysis Using IntramolecularJournal of the American Chemical Society · 2025Article
- Predicting Selectivity with a Bifurcating Surface: Inaccurate Model or Inaccurate Statistics of Dynamics?The journal of physical chemistry. A · 2024Article
- Transition State Analysis of Key Steps in Dual Photoredox-Cobalt-Catalyzed Elimination of Alkyl Bromides.ACS catalysis · 2024Article
- Enzymatic Control over Reactive Intermediates Enables Direct Oxidation of Alkenes to Carbonyls by a P450 Iron-Oxo Species.Journal of the American Chemical Society · 2022Article
- Novel Reagent Space: Identifying Unorderable but Readily Synthesizable Building Blocks.ACS medicinal chemistry letters · 2021Article
- Bifurcating reactions: distribution of products from energy distribution in a shared reactive mode.Chemical science · 2021Article
- Energy Read-out as a Probe of Kinetically Hidden Transition States.Organic letters · 2021Article
- Rapid Evaluation of the Mechanism of Buchwald-Hartwig Amination and Aldol Reactions Using IntramolecularACS catalysis · 2021Article
- Vibrationally Hot and Cold Triplets. Sensitizer-Dependent Dynamics and Localized Vibrational Promotion of a Di-π-methane Rearrangement.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
- Unusual KIE and dynamics effects in the Fe-catalyzed hetero-Diels-Alder reaction of unactivated aldehydes and dienes.Nature communications · 2020Article
- Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions.Communications chemistry · 2020Article
- MonoauratedChemical science · 2019Article
- Relaxation Dispersion NMR to Reveal Fast Dynamics in Brønsted Acid Catalysis: Influence of Sterics and H-Bond Strength on Conformations and Substrate Hopping.Journal of the American Chemical Society · 2019Article
Corrections and comments
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Authors and funding
2 authors.
Funding
Abstract
Any long-lived chemical structure in solution is subject to statistical energy equilibration, so the history of any specific structure does not affect its subsequent reactions. This is not true for very short-lived intermediates because energy equilibration takes time. Here, this idea is applied to achieve the 'energy labelling' of a reactive intermediate. The selectivity of the ring-opening α-cleavage reaction of the 1-methylcyclobutoxy radical is found here to vary broadly depending on how the radical was formed. Reactions that provide little excess energy to the intermediate lead to a high selectivity in the subsequent cleavage (measured as a kinetic isotope effect), whereas reactions that provide more excess energy to the intermediate exhibit a lower selectivity. Accounting for the expected excess energy allows the prediction of the observed product ratios and, in turn, the product ratios can be used to determine the energy present in an intermediate.
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Registered trials
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