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Burger, Veronika ; Franta, Maximilian ; O‘Donoghue, AnnMarie C. ; Ofial, Armin R. ; Gschwind, Ruth M. ; Zipse, Hendrik

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 typeArticle
Journal or Publication TitleThe Journal of Organic Chemistry
Publisher:American Chemical Society (ACS)
Date30 January 2025
InstitutionsChemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind
Projects
Funded by: Deutsche Forschungsgemeinschaft (DFG) (426795949)
Identification Number
ValueType
10.1021/acs.joc.4c02668DOI
Dewey Decimal Classification500 Science > 540 Chemistry & allied sciences
StatusPublished
RefereedYes, this version has been refereed
Created at the University of RegensburgPartially
URN of the UB Regensburgurn:nbn:de:bvb:355-epub-748126
Item ID74812

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