A chiral pentanidium and pyridinyl-sulphonamide ion pair as an enantioselective organocatalyst for Steglich rearrangement

Yang, Ziqi; Xu, Chaoran; Zhou, Xianxian; Cheong, Choon Boon; Kee, Choon Wee; Tan, Choon-Hong

doi:10.1039/d3sc04397e

Chem. Sci.

2023

DOI: 10.1039/d3sc04397e

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A chiral pentanidium and pyridinyl-sulphonamide ion pair as an enantioselective organocatalyst for Steglich rearrangement

Ziqi Yang,

Chaoran Xu,

Xianxian Zhou

et al.

Abstract: We report the successful development of a stable chiral pentanidium pyridinyl-sulphonamide ion pair as a nucleophilic organocatalyst for asymmetric Steglich rearrangement.

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2024

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Cited by 2 publications

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Exploiting Ion-Pairing Interactions for Fast and Controlled Ring-Opening Polymerization of rac-β-Butyrolactone at Room Temperature with Dinuclear Sodium and Potassium Catalysts

Chen,

Zhang,

Zuo

et al. 2024

Macromolecules

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Poly(β-hydroxybutyrate) (PHB) is one of the best candidates as a sustainable plastic material for a circular economy due to its biorenewability, biodegradability, and biocompatibility. Compared with other metal catalysts that have made great progress, the highly active and controlled polymerization of rac-β-hydroxybutyrate (rac-BBL) for the synthesis of PHB using sodium and potassium catalysts at room temperature is still rarely reported and remains a great challenge. In this contribution, a series of novel and adjustable dinuclear sodium and potassium ion-pair catalysts were designed and synthesized, in which the optimized catalyst 2 allows for fast ring-opening polymerization (ROP) of rac-BBL (turnover frequency up to 99 h −1 ) in bulk at room temperature to prepare PHB with predictable molar mass and excellent molecular weight distribution (D̵ = 1.06). The effect of the structure of catalysts such as the type of alkali metal ion, the electronic and steric effect of substituent groups, and the size of countercation on the ROP activity was systematically investigated. Single crystal X-ray diffraction, NMR, MALDI-TOF, and DTF calculations were utilized to uncover that the presence of the ion-pairing interactions within sodium-and potassium-based catalysts is considered to be crucial for both enhancing the nucleophilicity and reducing the alkalinity of the initiator (phenolate anion)/chainend (carboxylate anion) during catalysis, thus effectively promoting polymerization reaction and suppressing adverse side reaction (e.g., deprotonation, base-promoted elimination, and chain scission) for gaining PHB with molecular weight (M n ) up to 51 kg mol −1 . This study provides fruitful information to deeply understand the catalytic role of ion-pairing interactions within sodium-and potassium-based catalysts, which would contribute to the design of novel, efficient, and eco-friendly catalysts for the polymerization of the other cyclic esters.

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Exploiting Ion-Pairing Interactions for Fast and Controlled Ring-Opening Polymerization of rac-β-Butyrolactone at Room Temperature with Dinuclear Sodium and Potassium Catalysts

Chen,

Zhang,

Zuo

et al. 2024

Macromolecules

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Modular access to diarylmethyl sulfonamides via visible light-promoted cross-coupling reactions

Mei,

Zhang,

Jiang

et al. 2024

Chem. Commun.

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A chiral pentanidium and pyridinyl-sulphonamide ion pair as an enantioselective organocatalyst for Steglich rearrangement

Abstract: We report the successful development of a stable chiral pentanidium pyridinyl-sulphonamide ion pair as a nucleophilic organocatalyst for asymmetric Steglich rearrangement.

Cited by 2 publications

References 54 publications

Exploiting Ion-Pairing Interactions for Fast and Controlled Ring-Opening Polymerization of rac-β-Butyrolactone at Room Temperature with Dinuclear Sodium and Potassium Catalysts

Exploiting Ion-Pairing Interactions for Fast and Controlled Ring-Opening Polymerization of rac-β-Butyrolactone at Room Temperature with Dinuclear Sodium and Potassium Catalysts

Modular access to diarylmethyl sulfonamides via visible light-promoted cross-coupling reactions

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