Serena Moccia, Massimo Christian D' Alterio, Eugenio Romano, Claudio De Rosa, Giovanni Talarico
{"title":"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","authors":"Serena Moccia, Massimo Christian D' Alterio, Eugenio Romano, Claudio De Rosa, Giovanni Talarico","doi":"10.1002/marc.202400733","DOIUrl":null,"url":null,"abstract":"<p><p>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 (%V<sub>Bur</sub>) 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 %V<sub>Bur</sub> 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.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":null,"pages":null},"PeriodicalIF":4.2000,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Stereoselectivity Control Interplay in Racemic Lactide Polymerization by Achiral Al-Salen Complexes.\",\"authors\":\"Serena Moccia, Massimo Christian D' Alterio, Eugenio Romano, Claudio De Rosa, Giovanni Talarico\",\"doi\":\"10.1002/marc.202400733\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>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 (%V<sub>Bur</sub>) 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 %V<sub>Bur</sub> 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.</p>\",\"PeriodicalId\":205,\"journal\":{\"name\":\"Macromolecular Rapid Communications\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.2000,\"publicationDate\":\"2024-10-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecular Rapid Communications\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/marc.202400733\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecular Rapid Communications","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/marc.202400733","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
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.
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.