Mechanism‐Based Approach to Reagent Selection for Oxidative Carbon−Hydrogen Bond Cleavage Reactions
| Autor: | Lin Zhou, Jenna Miller, Peng Liu, Paul E. Floreancig |
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| Rok vydání: | 2021 |
| Předmět: |
Steric effects
Reaction mechanism Hydride Organic Chemistry Hydrogen Bonding Carbon–hydrogen bond activation General Chemistry Carbocation Carbon Catalysis Reaction rate Oxidative Stress chemistry.chemical_compound chemistry Computational chemistry Reagent Indicators and Reagents Reactivity (chemistry) Oxidation-Reduction |
| Zdroj: | Chemistry – A European Journal. 28 |
| ISSN: | 1521-3765 0947-6539 |
| Popis: | Numerous hydride-abstracting agents generate the same cationic intermediate, but substrate features such as intermediate cation stability, oxidation potential, and steric environment can influence reaction rates in an oxidant-dependent manner. This manuscript provides experimental data to illustrate the role that structural features play in the kinetics of hydride abstraction reactions with commonly used quinone-, oxoammonium ion-, and carbocation- based oxidants. Computational studies of the transition state structures and energies explain these results and energy decomposition analysis calculations reveal unique sensitivities to electrostatic attraction and steric repulsions. Rigorous rate studies of select reactions validated the capacity of the calculations to predict reactivity trends. Additionally, kinetics studies demonstrate the potential for product inhibition in DDQ-mediated reactions. These studies provide a clear guide to select the optimal oxidant for structurally disparate substrates and lead to predictions of reactivity that were validated experimentally. |
| Databáze: | OpenAIRE |
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