Jaroslav Pochobradský , Jan Bartáček , Jiří Váňa , Jan Svoboda , Tomáš Hlavatý , Jhonatan Rodriguez-Pereira , Miloš Sedlák
{"title":"聚合物支持的双CH功能化MPAA-Pd催化剂:匹配均相效率,同时揭示可回收性限制","authors":"Jaroslav Pochobradský , Jan Bartáček , Jiří Váňa , Jan Svoboda , Tomáš Hlavatý , Jhonatan Rodriguez-Pereira , Miloš Sedlák","doi":"10.1016/j.reactfunctpolym.2025.106478","DOIUrl":null,"url":null,"abstract":"<div><div>MPAA–Pd catalysts are widely used in C<img>H functionalization, but their heterogenization remains underexplored. We developed polymer-supported MPAA–Pd catalysts by copolymerization and post-functionalization of <em>N</em>-acetyltyrosine derivatives. Under optimized conditions, they matched homogeneous performance across 13 substrates (up to 64 % yield) and showed ∼29 % lower residual Pd in the product (2527 ± 425 vs. 3556 ± 479 ppm). However, recyclability was poor: yield dropped from 65 % to 16 % in the second cycle due to Pd leaching. XPS confirmed partial Pd(II) reduction during turnover, while the polymer remained chemically intact. The results reveal that Pd–carboxylate coordination is inherently unstable under basic conditions, limiting the viability of this immobilization strategy. This work illustrates the value of heterogenized systems as mechanistic probes, even when synthetic utility proves limited.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"217 ","pages":"Article 106478"},"PeriodicalIF":5.1000,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Polymer-supported MPAA–Pd catalysts for dual CH functionalization: Matching homogeneous efficiency while revealing recyclability limits\",\"authors\":\"Jaroslav Pochobradský , Jan Bartáček , Jiří Váňa , Jan Svoboda , Tomáš Hlavatý , Jhonatan Rodriguez-Pereira , Miloš Sedlák\",\"doi\":\"10.1016/j.reactfunctpolym.2025.106478\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>MPAA–Pd catalysts are widely used in C<img>H functionalization, but their heterogenization remains underexplored. We developed polymer-supported MPAA–Pd catalysts by copolymerization and post-functionalization of <em>N</em>-acetyltyrosine derivatives. Under optimized conditions, they matched homogeneous performance across 13 substrates (up to 64 % yield) and showed ∼29 % lower residual Pd in the product (2527 ± 425 vs. 3556 ± 479 ppm). However, recyclability was poor: yield dropped from 65 % to 16 % in the second cycle due to Pd leaching. XPS confirmed partial Pd(II) reduction during turnover, while the polymer remained chemically intact. The results reveal that Pd–carboxylate coordination is inherently unstable under basic conditions, limiting the viability of this immobilization strategy. This work illustrates the value of heterogenized systems as mechanistic probes, even when synthetic utility proves limited.</div></div>\",\"PeriodicalId\":20916,\"journal\":{\"name\":\"Reactive & Functional Polymers\",\"volume\":\"217 \",\"pages\":\"Article 106478\"},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2025-09-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Reactive & Functional Polymers\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S138151482500330X\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Reactive & Functional Polymers","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S138151482500330X","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Polymer-supported MPAA–Pd catalysts for dual CH functionalization: Matching homogeneous efficiency while revealing recyclability limits
MPAA–Pd catalysts are widely used in CH functionalization, but their heterogenization remains underexplored. We developed polymer-supported MPAA–Pd catalysts by copolymerization and post-functionalization of N-acetyltyrosine derivatives. Under optimized conditions, they matched homogeneous performance across 13 substrates (up to 64 % yield) and showed ∼29 % lower residual Pd in the product (2527 ± 425 vs. 3556 ± 479 ppm). However, recyclability was poor: yield dropped from 65 % to 16 % in the second cycle due to Pd leaching. XPS confirmed partial Pd(II) reduction during turnover, while the polymer remained chemically intact. The results reveal that Pd–carboxylate coordination is inherently unstable under basic conditions, limiting the viability of this immobilization strategy. This work illustrates the value of heterogenized systems as mechanistic probes, even when synthetic utility proves limited.
期刊介绍:
Reactive & Functional Polymers provides a forum to disseminate original ideas, concepts and developments in the science and technology of polymers with functional groups, which impart specific chemical reactivity or physical, chemical, structural, biological, and pharmacological functionality. The scope covers organic polymers, acting for instance as reagents, catalysts, templates, ion-exchangers, selective sorbents, chelating or antimicrobial agents, drug carriers, sensors, membranes, and hydrogels. This also includes reactive cross-linkable prepolymers and high-performance thermosetting polymers, natural or degradable polymers, conducting polymers, and porous polymers.
Original research articles must contain thorough molecular and material characterization data on synthesis of the above polymers in combination with their applications. Applications include but are not limited to catalysis, water or effluent treatment, separations and recovery, electronics and information storage, energy conversion, encapsulation, or adhesion.