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Pyridinamide Ion Pairs: Design Principles for Super-Nucleophiles in Apolar Organic Solvents
Burger, Veronika, Franta, Maximilian, O‘Donoghue, AnnMarie C., Ofial, Armin R., Gschwind, Ruth M.
and Zipse, Hendrik
(2025)
Pyridinamide Ion Pairs: Design Principles for Super-Nucleophiles in Apolar Organic Solvents.
The Journal of Organic Chemistry.
Date of publication of this fulltext: 04 Feb 2025 05:26
Article
DOI to cite this document: 10.5283/epub.74812
Abstract
A comprehensive analytical protocol combining conductivity, diffusion-ordered NMR (DOSY), and photometric kinetic measurements is employed to analyze the nucleophilic reactivity of pyridinamide ion pairs in low-polarity organic solvents. The association patterns of these systems are found to strongly depend on cation size, with larger cations favoring the formation of cationic triple ion sandwich ...
A comprehensive analytical protocol combining conductivity, diffusion-ordered NMR (DOSY), and photometric kinetic measurements is employed to analyze the nucleophilic reactivity of pyridinamide ion pairs in low-polarity organic solvents. The association patterns of these systems are found to strongly depend on cation size, with larger cations favoring the formation of cationic triple ion sandwich complexes together with free and highly nucleophilic anions. Kinetic studies using the ionic strength-controlled benzhydrylium method demonstrate that pyridinamide ions exhibit significantly higher nucleophilicities as compared to established organocatalysts, particularly in low-polarity solvents. Nucleophilicities are furthermore found to correlate well with Brønsted basicities measured in water and with Lewis basicities calculated in dichloromethane. Taken together, these findings provide quantitative guidelines for the future design of highly active Lewis base catalysts.
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Details
| Item type | Article | ||||
| Journal or Publication Title | The Journal of Organic Chemistry | ||||
| Publisher: | American Chemical Society (ACS) | ||||
|---|---|---|---|---|---|
| Date | 30 January 2025 | ||||
| Institutions | Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind | ||||
| Projects |
Funded by:
Deutsche Forschungsgemeinschaft (DFG)
(426795949)
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| Identification Number |
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| Dewey Decimal Classification | 500 Science > 540 Chemistry & allied sciences | ||||
| Status | Published | ||||
| Refereed | Yes, this version has been refereed | ||||
| Created at the University of Regensburg | Partially | ||||
| URN of the UB Regensburg | urn:nbn:de:bvb:355-epub-748126 | ||||
| Item ID | 74812 |
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