<p>Ionic interactions between DNA phosphates and positively charged amino acid residues in aqueous environments are ubiquitous and essential across all biological systems. Such interactions are readily disrupted by polar solvents according to Coulomb’s law, which accounts for the predominant use of non-polar or weakly polar organic solvents in chiral phosphate-mediated asymmetric organocatalysis. This intriguing discrepancy prompted us to exploit the possibility of conducting asymmetric catalysis in water with intrinsically chiral and abundant DNA phosphates. Here we experimentally and computationally demonstrate that DNA phosphates play a critical role in rate acceleration and stereoinduction through ion-pairing interactions with cationic reagents, featuring a cation-dependent dynamic and adaptive nature of the DNA catalyst rarely seen in highly specific enzymatic systems.</p><p></p>

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DNA phosphates are effective catalysts for asymmetric ion-pairing catalysis in water

  • Zhaoyang Li,
  • Yang Zheng,
  • Qi Zhao,
  • Yihan Li,
  • Adon Yap,
  • Xinglong Zhang,
  • Ru-Yi Zhu

摘要

Ionic interactions between DNA phosphates and positively charged amino acid residues in aqueous environments are ubiquitous and essential across all biological systems. Such interactions are readily disrupted by polar solvents according to Coulomb’s law, which accounts for the predominant use of non-polar or weakly polar organic solvents in chiral phosphate-mediated asymmetric organocatalysis. This intriguing discrepancy prompted us to exploit the possibility of conducting asymmetric catalysis in water with intrinsically chiral and abundant DNA phosphates. Here we experimentally and computationally demonstrate that DNA phosphates play a critical role in rate acceleration and stereoinduction through ion-pairing interactions with cationic reagents, featuring a cation-dependent dynamic and adaptive nature of the DNA catalyst rarely seen in highly specific enzymatic systems.