Solubility-Equilibrium-Assisted Kinetic Resolution Polymerization toward Isotactic Polyesters Containing Axial Chirality

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Journal of the American Chemical Society Pub Date : 2024-12-16 DOI:10.1021/jacs.4c14778
Qing Cao, Hua-Zhong Fan, Min Xie, Zhongzheng Cai, Jian-Bo Zhu
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Abstract

High-level control over polymer stereochemistry leverages the fine-tuning of material properties, but it is still a formidable challenge in synthetic polymer chemistry. Herein we prepared a new class of salph yttrium catalysts bearing axially chiral binaphthyl moieties for axially stereocontrolled polymerization of rac-Me-DBO. (S)-Y3-bearing bulkier binaphthyl units accomplished moderate isoselectivity via kinetic resolution polymerization, affording P(Me-BDO) with a Pm of up to 0.80. Remarkably, exploiting the solubility equilibrium to maintain a constant for the concentration of two enantiopure monomer pairs in the solution state contributed to a boost in polymerization isoselectivity and furnished isotactic P(Me-DBO) products with a Pm of up to 0.93. Detailed mechanistic investigations supported our solubility-equilibrium shifting hypothesis. This solubility-equilibrium-assisted kinetic resolution polymerization strategy was expected to become a versatile platform to improve stereocontrol without de novo catalyst design.

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溶解度-平衡辅助的动力学解析聚合反应,向含有轴向手性的异构聚酯转化
对聚合物立体化学的高度控制有助于对材料特性进行微调,但这仍然是合成聚合物化学领域的一项艰巨挑战。在此,我们制备了一类新型盐基钇催化剂,该催化剂含有轴向手性二萘基,可用于rac-Me-DBO 的轴向立体控制聚合。(S)-Y3含有较膨松的二萘基单元,通过动力学解析聚合实现了适度的等选择性,可得到Pm高达0.80的P(Me-BDO)。值得注意的是,利用溶解度平衡来保持溶液状态中两对映纯单体对的浓度恒定,有助于提高聚合的等选择性,并产生 Pm 值高达 0.93 的异构 P(Me-DBO)产品。详细的机理研究支持了我们的溶解度-平衡移动假设。这种溶解度-平衡辅助动力学解析聚合策略有望成为一种通用平台,无需重新设计催化剂即可改善立体控制。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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