Highly Nucleophilic Pyridinamide Anions in Apolar Organic Solvents due to Asymmetric Ion Pair Association.

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 dichlorom

SUBMITTER: Burger V 

PROVIDER: S-EPMC11826998 | biostudies-literature | 2025 Feb

REPOSITORIES: biostudies-literature