Chen Chen, Janoszka Nicole, Wong Chin Ken, Gramse Christian, Weberskirch Ralf, Gröschel André H
Physical Chemistry, University of Münster, Corrensstraße 28-30, 48149, Münster, Germany.
Faculty of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn-Straße 6, 44227, Dortmund, Germany.
Angew Chem Int Ed Engl. 2021 Jan 4;60(1):237-241. doi: 10.1002/anie.202008104. Epub 2020 Oct 28.
We report on the synthesis of core-shell microparticles (CSMs) with an acid catalyst in the core and a base catalyst in the shell by surfactant-free emulsion polymerization (SFEP). The organocatalytic monomers were separately copolymerized in three synthetic steps allowing the spatial separation of incompatible acid and base catalysts within the CSMs. Importantly, a protected and thermo-decomposable sulfonate monomer was used as acid source to circumvent the neutralization of the base catalyst during shell formation, which was key to obtain stable, catalytically active CSMs. The catalysts showed excellent performance in an established one-pot model cascade reaction in various solvents (including water), which involved an acid-catalyzed deacetalization followed by a base-catalyzed Knoevenagel condensation. The CSMs are easily recycled, modified, and their synthesis is scalable, making them promising candidates for organocatalytic applications.
我们报道了通过无表面活性剂乳液聚合(SFEP)合成核壳微粒(CSM),其核中含有酸催化剂,壳中含有碱催化剂。有机催化单体在三个合成步骤中分别共聚,从而实现了不相容的酸和碱催化剂在CSM内的空间分离。重要的是,使用了一种受保护且可热分解的磺酸盐单体作为酸源,以避免在壳形成过程中碱催化剂被中和,这是获得稳定的、具有催化活性的CSM的关键。这些催化剂在各种溶剂(包括水)中的既定一锅法模型级联反应中表现出优异的性能,该反应涉及酸催化的脱缩醛反应,随后是碱催化的Knoevenagel缩合反应。CSM易于回收、改性,并且其合成具有可扩展性,使其成为有机催化应用中有前景的候选者。