ArticlePhysical chemistry chemical physics : PCCP2021
Origin of asynchronicity in Diels-Alder reactions.
Article in Physical chemistry chemical physics : PCCP, 2021. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 14 papers.
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14 citing papers in PubMed, 42 citations in OpenAlex.
- PyOrbb-Automated Analyses of Orbital-Interaction Mechanisms.Journal of computational chemistry · 2026Article
- Insights into Tetrazine-Benzene Cycloadditions.The journal of physical chemistry. A · 2026Article
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- Straightforward Access to Pentafluorosulfanylated Phenols and Aminophenols via [4 + 2] Diels-Alder Cycloaddition Reaction.ACS organic & inorganic Au · 2025Article
- How to search for and reveal a hidden intermediate? The ELF topological description of non-synchronicity in double proton transfer reactions under oriented external electric field.Journal of molecular modeling · 2024Article
- Computational Organic Chemistry: The Frontier for Understanding and Designing Bioorthogonal Cycloadditions.Topics in current chemistry (Cham) · 2024Review
- Computational molecular refinement to enhance enantioselectivity by reinforcing hydrogen bonding interactions in major reaction pathway.Chemical science · 2023Article
- Substituent Effects in Bioorthogonal Diels-Alder Reactions of 1,2,4,5-Tetrazines.Chemistry (Weinheim an der Bergstrasse, Germany) · 2023Article
- Additivity of Diene Substituent Gibbs Free Energy Contributions for Diels-Alder Reactions between MeACS omega · 2023Article
- How Bases Catalyze Diels-Alder Reactions.Chemistry (Weinheim an der Bergstrasse, Germany) · 2023Article
- ηChemistry, an Asian journal · 2023Article
- How Ionization Catalyzes Diels-Alder Reactions.Chemistry (Weinheim an der Bergstrasse, Germany) · 2022Article
- Understanding the Mechanism of Diels-Alder Reactions with Anionic Dienophiles: A Systematic Comparison of [ECX]Inorganic chemistry · 2022Article
- New Insights into the (A)Synchronicity of Diels-Alder Reactions: A Theoretical Study Based on the Reaction Force Analysis and Atomic Resolution of Energy Derivatives.Molecules (Basel, Switzerland) · 2022Article
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Authors and funding
3 authors at 2 institutions in 1 country.
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No grant is acknowledged in the PubMed record.
Abstract
Asynchronicity in Diels-Alder reactions plays a crucial role in determining the height of the reaction barrier. Currently, the origin of asynchronicity is ascribed to the stronger orbital interaction between the diene and the terminal carbon of an asymmetric dienophile, which shortens the corresponding newly formed C-C bond and hence induces asynchronicity in the reaction. Here, we show, using the activation strain model and Kohn-Sham molecular orbital theory at ZORA-BP86/TZ2P, that this rationale behind asynchronicity is incorrect. We, in fact, found that following a more asynchronous reaction mode costs favorable HOMO-LUMO orbital overlap and, therefore, weakens (not strengthens) these orbital interactions. Instead, it is the Pauli repulsion that induces asynchronicity in Diels-Alder reactions. An asynchronous reaction pathway also lowers repulsive occupied-occupied orbital overlap which, therefore, reduces the unfavorable Pauli repulsion. As soon as this mechanism of reducing Pauli repulsion dominates, the reaction begins to deviate from synchronicity and adopts an asynchronous mode. The eventual degree of asynchronicity, as observed in the transition state of a Diels-Alder reaction, is ultimately achieved when the gain in stability, as a response to the reduced Pauli repulsion, balances with the loss of favorable orbital interactions.
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