手性 Al-Salen 复合物在外消旋内酰胺聚合过程中的立体选择性控制相互作用

IF 4.2 3区 化学 Q2 POLYMER SCIENCE Macromolecular Rapid Communications Pub Date : 2024-10-22 DOI:10.1002/marc.202400733
Serena Moccia, Massimo Christian D' Alterio, Eugenio Romano, Claudio De Rosa, Giovanni Talarico
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引用次数: 0

摘要

通过 DFT 计算结合分子描述符(%VBur)和活化应变模型(ASM-NEDA)分析,解释了非手性铝基催化剂促进外消旋内酰胺(rac-LA)开环聚合(ROP)过程中立体控制的起源。所提出的链端控制 (CEC) 模型表明,配体框架采用了模仿对映体位点控制 (ESC) 的手性构型,同时还结合了对最后插入单体单元的控制。研究发现,铝中心周围的配体包裹模式由单体构型(R,R-LA 和 S,S-LA)决定。只有考虑到配体的动态特征及其立体影响,才能实现与实验数据的良好相关性,这一点在 %VBur 立体图和 ASM-NEDA 分析中得到了强调。了解 ESC 和 CEC 的相互作用是获得立体选择性 ROP 聚合以合成具有定制特性的生物可降解材料的一个重要目标。
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Stereoselectivity Control Interplay in Racemic Lactide Polymerization by Achiral Al-Salen Complexes.

The origin of stereocontrol in ring opening polymerization (ROP) of racemic lactide (rac-LA) promoted by achiral aluminium-based catalysts has been explained through DFT calculations combined with a molecular descriptor (%VBur) and the activation strain model (ASM-NEDA) analysis. The proposed chain end control (CEC) model suggests that the ligand framework adopts a chiral configuration mimicking the enantiomorphic site control (ESC) while also incorporating control of the last inserted monomer unit. It is found that the ligand wrapping mode around the aluminium centre is dictated by the monomer configuration (R,R-LA and S,S-LA). A good correlation with experimental data is achieved only when accounting for the ligand dynamic features and its steric influences, as highlighted by %VBur steric maps and ASM-NEDA analysis. Understanding the ESC and CEC interplay is an important target for obtaining stereoselective ROP polymerization for the synthesis of biodegradable materials with tailored properties.

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来源期刊
Macromolecular Rapid Communications
Macromolecular Rapid Communications 工程技术-高分子科学
CiteScore
7.70
自引率
6.50%
发文量
477
审稿时长
1.4 months
期刊介绍: Macromolecular Rapid Communications publishes original research in polymer science, ranging from chemistry and physics of polymers to polymers in materials science and life sciences.
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