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March 4, 2026The Journal of Organic Chemistry0 citations

Pillararene-Catalyzed Kemp Elimination: High Efficiency through Orthogonal Self-Sorting Binding and Ion Modulation

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DZDejun ZhangJZJintian ZhongPYPei Yu

Key Points

  • The study aims to improve the efficiency of supramolecular catalysis using pillar[6]arenes in the Kemp elimination reaction.
  • Utilized water-soluble pillar[6]arenes with quaternary ammonium groups as catalysts
  • Conducted Kemp elimination reactions of 1,2-benzisoxazole in aqueous conditions
  • Examined the effects of pH and ion modulation on reaction rates
  • Assessed recycling potential of the catalyst
  • Achieved a kcat/kuncat ratio of up to 1.5 × 10^5 at pH 8
  • Substrate preorganization enhanced reaction rates due to selective ionic interactions
  • Showed robust catalysis at pH 6-7 with sustainable recycling capabilities

Abstract

Enhancing the efficiency and versatility of supramolecular catalysis remains a central research goal. Water-soluble pillar6arenes (H1), per-substituted with quaternary ammonium groups, catalyze the aqueous-phase Kemp elimination of 1,2-benzisoxazole (R1), achieving kcat/kuncat ratio up to 1.5 × 105 at pH 8, surpassing previously reported macrocycles for the reaction and rivaling the remarkable rate enhancements (up to 2 × 105-fold) of coordination cages. Orthogonal self-sorting binding enables R1 to anchor in the hydrophobic cavity while OH- enriches at the positively charged portals, facilitating substrate preorganization and enrichment. Ions, including OH-, selectively weaken the binding of the anionic product while strengthening substrate R1 association, mitigating product inhibition and boosting turnover. Robust catalysis at pH 6-7 and recyclability provide a sustainable, enzyme-mimetic catalytic strategy.

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Cite This Study

Zhang et al. (2026) studied this question.

synapsesocial.com/papers/69a7cd2ad48f933b5eed9536https://doi.org/10.1021/acs.joc.5c02889
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