ArticleJournal of the American Chemical Society2025
Highly Nucleophilic Pyridinamide Anions in Apolar Organic Solvents due to Asymmetric Ion Pair Association.
Article in Journal of the American Chemical Society, 2025. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 3 papers.
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Who cites it
3 citing papers in PubMed.
- Charge-enhanced pyridyl trifluoroborate organocatalysts: crystal structures and reactivity.Acta crystallographica. Section C, Structural chemistry · 2026Article
- From Oxygen to Tellurium: The Impact of the Chalcogen on Nucleophilicities and Basicities of Isochalcogenourea Catalysts.Angewandte Chemie (International ed. in English) · 2025Article
- Pyridinamide Ion Pairs: Design Principles for Super-Nucleophiles in Apolar Organic Solvents.The Journal of organic chemistry · 2025Article
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Authors and funding
5 authors.
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Abstract
Free ions in organic solvents of low polarity would be valuable tools for the activation of low-reactivity substrates. However, the formation of unreactive ion pairs at concentrations relevant for synthesis has prevented the success of this concept so far. On the example of highly nucleophilic pyridinamide phosphonium salts in dichloromethane, we show that asymmetric aggregation offers a solution to this general problem. A combination of conductivity, diffusion-ordered NMR (DOSY), and kinetic measurements utilizing a refined ionic strength-controlled benzhydrylium ion methodology enables unique insight into the aggregation/association state of the ions and the nucleophilicity of the involved anions. This approach reveals that pyridinamide tetraphenylphosphonium salts aggregate in dichloromethane solution asymmetrically to form sandwich-type cations and anions together with their free counterions. The nucleophilicity of free pyridinamide ions exceeds that of the neutral reference nucleophile 9-azajulolidine (TCAP) by up to 2 orders of magnitude. Based on these results, we suggest that asymmetric aggregation in organic solvents of low polarity might be a general pathway to boost the reactivity of anionic nucleophiles.
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