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Oxidation Potential Gap (ΔEox ): The Hidden Parameter in Redox Chemistry
Kazuhiro Okamoto1,2, Naoki Shida2, Haruka Morizumi1
1Department of Applied Biological Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo, 183-8509, Japan.
Angewandte Chemie (International Ed. in English)
|May 24, 2022
Summary
The oxidation potential gap (ΔEox) predicts oxidative coupling efficiency in aromatic rings. Tuning this gap enables rational synthesis of complex structures like phenanthridones.
Area of Science:
- Organic Chemistry
- Computational Chemistry
- Reaction Mechanism
Background:
- Oxidative biaryl coupling of electronically diverse aryls often fails.
- The key factors governing coupling efficiency lack systematic theoretical investigation.
Purpose of the Study:
- To identify and validate a predictive parameter for intramolecular oxidative coupling efficiency.
- To explore the relationship between electronic properties and reaction outcomes.
Main Methods:
- Theoretical analysis using computational chemistry to study reaction mechanisms.
- Experimental validation of proposed theoretical parameters.
- Synthesis of phenanthridone skeletons.
Main Results:
- The oxidation potential gap (ΔEox) is identified as a crucial parameter for predicting coupling efficiency.
- Coupling efficiency correlates with the activation energy (ΔE≠) for C-C bond formation in radical cation intermediates.
- ΔE≠ is shown to correlate with ΔEox.
Conclusions:
- The oxidation potential gap (ΔEox) provides a reliable metric for assessing intramolecular oxidative coupling feasibility.
- Rational tuning of ΔEox through auxiliary groups allows for controlled synthesis of phenanthridone structures.
- This work offers a theoretical framework for optimizing oxidative coupling reactions involving electronically differentiated aromatic systems.
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