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Abstract <p>To address the challenges of poor recyclability and stability in small-molecule catalysts for asym­metric synthesis, this study developed a helical polymer catalyst with precisely engineered pyrrolidine catalytic centers through rational molecular design. A novel helical polymer catalyst (<b>Poly-1</b><sub><b>200</b></sub>) was successfully synthesized via palladium-initiated isocyanide monomer polymerization followed by Boc-deprotection. This catalyst demonstrated outstanding stereocontrol in isopropyl alcohol without additives. Using cyclohexanone and 4-nitrobenzaldehyde as model substrates, the reaction achieved 98% enantiomeric excess (<i>ee</i>). Notably, substituting cyclohexanone with cyclopentanone and employing trifluoromethyl-substituted benzaldehydes (4-CF<sub>3</sub> or 2-CF<sub>3</sub>) significantly enhanced stereoselectivity, yielding 99% <i>ee</i> with improved diastereomeric ratio (<i>dr</i>) values of 72:28 and 67:33, respectively. Importantly, the catalyst retained 94% <i>ee</i> and over 93% recovery rate after three cycles, overcoming the technical bottleneck of poor recyclability in conventional organocatalysts. This work provides an innovative design paradigm for developing highly efficient and recyclable polymer-based catalytic systems, merging macromolecular engineering with advanced stereochemical control.</p>

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Rational Design of Recyclable Helical Polymeric Catalysts Bearing Pyrrolidine Motifs for High-Efficiency Asymmetric Aldol Reactions

  • 期刊论文

  • 发表日期：

    2025年12月1日

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  • Chaoxing Chen,
  • Shuyi Wang,
  • Chonglong Li

摘要

Abstract

To address the challenges of poor recyclability and stability in small-molecule catalysts for asym­metric synthesis, this study developed a helical polymer catalyst with precisely engineered pyrrolidine catalytic centers through rational molecular design. A novel helical polymer catalyst (Poly-1200) was successfully synthesized via palladium-initiated isocyanide monomer polymerization followed by Boc-deprotection. This catalyst demonstrated outstanding stereocontrol in isopropyl alcohol without additives. Using cyclohexanone and 4-nitrobenzaldehyde as model substrates, the reaction achieved 98% enantiomeric excess (ee). Notably, substituting cyclohexanone with cyclopentanone and employing trifluoromethyl-substituted benzaldehydes (4-CF3 or 2-CF3) significantly enhanced stereoselectivity, yielding 99% ee with improved diastereomeric ratio (dr) values of 72:28 and 67:33, respectively. Importantly, the catalyst retained 94% ee and over 93% recovery rate after three cycles, overcoming the technical bottleneck of poor recyclability in conventional organocatalysts. This work provides an innovative design paradigm for developing highly efficient and recyclable polymer-based catalytic systems, merging macromolecular engineering with advanced stereochemical control.