Asymmetric Aldol Reactions Catalyzed by Polymeric Self-Assembly with Side-Chain Dipeptide Pendants

IF 5.1 Q1 POLYMER SCIENCE ACS Macro Letters Pub Date : 2024-05-09 DOI:10.1021/acsmacrolett.4c00185

Tamanna Mallick, Debgopal Jana, Alakesh Bisai* and Priyadarsi De*,

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Abstract

To explore the role of proline amide moieties in polymer-supported organocatalysts, side-chain l-proline–l-alanine (Pro-Ala) dipeptide-containing block copolymers were synthesized, and their catalytic potential for the aldol reaction was explored. The dipeptide monomer (Boc-Pro-Ala-HEMA) was polymerized to prepare block copolymers in the presence of hydrophilic poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA) and hydrophobic poly(methyl methacrylate) (PMMA) macro-chain transfer agents. Boc group expulsion from the block copolymers produced double hydrophilic PPEGMA-b-P(Pro-Ala-HEMA) (1b) and amphiphilic PMMA-b-P(Pro-Ala-HEMA) (1c) polymers. The solution behaviors of the polymers were studied by various physical techniques, which showed the formation of self-assembled aggregates of 1c in water and N,N-dimethylformamide (DMF)/water solvent mixtures. These polymers are used as organocatalysts during the aldol reaction of cyclohexanone and 4-nitrobenzaldehyde in different solvent polarities, catalyst loadings, temperatures, and reaction times. This work emphasizes superior catalytic activity of 1c at lower catalyst loadings (5%) while maintaining high conversion (95%) and enantioselectivity (94%) across multiple recycling cycles in DMF/water at a 3:1 ratio (v/v).

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聚合物自组装催化的不对称醛醇反应与侧链二肽附体。

为了探索脯氨酸酰胺分子在聚合物支撑的有机催化剂中的作用，我们合成了含侧链 l-脯氨酸-丙氨酸（Pro-Ala）二肽嵌段共聚物，并探讨了它们对醛醇反应的催化潜力。在亲水性聚（聚乙二醇甲醚甲基丙烯酸酯）（PPEGMA）和疏水性聚（甲基丙烯酸甲酯）（PMMA）大链转移剂存在下，二肽单体（Boc-Pro-Ala-HEMA）被聚合成嵌段共聚物。从嵌段共聚物中排出的 Boc 基团产生了双亲水性 PPEGMA-b-P(Pro-Ala-HEMA) (1b) 和双亲性 PMMA-b-P(Pro-Ala-HEMA) (1c) 聚合物。通过各种物理技术研究了这些聚合物的溶液行为，结果表明 1c 在水和 N,N-二甲基甲酰胺（DMF）/水溶剂混合物中形成了自组装聚集体。在环己酮和 4-硝基苯甲醛的醛醇反应中，这些聚合物在不同的溶剂极性、催化剂负载、温度和反应时间下用作有机催化剂。这项研究强调了 1c 在较低催化剂负载量（5%）下的卓越催化活性，同时在 DMF/ 水以 3:1 的比例（v/v）进行多次循环时仍能保持较高的转化率（95%）和对映选择性（94%）。

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来源期刊

ACS Macro Letters 化学-

CiteScore

10.40

自引率

3.40%

发文量

209

审稿时长

1 months

期刊介绍： ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science. With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.