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Activated Self-Resolution and Error-Correction in Catalytic Reaction Networks
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Organic chemistry.ORCID iD: 0000-0001-5298-4310
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Organic chemistry.ORCID iD: 0000-0002-1533-6514
2021 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 27, no 40, p. 10335-10340Article in journal (Refereed) Published
Abstract [en]

Understanding the emergence of function in complex reaction networks is a primary goal of systems chemistry and origin-of-life studies. Especially challenging is to create systems that simultaneously exhibit several emergent functions that can be independently tuned. In this work, a multifunctional complex reaction network of nucleophilic small molecule catalysts for the Morita-Baylis-Hillman (MBH) reaction is demonstrated. The dynamic system exhibited triggered self-resolution, preferentially amplifying a specific catalyst/product set out of a many potential alternatives. By utilizing selective reversibility of the products of the reaction set, systemic thermodynamically driven error-correction could also be introduced. To achieve this, a dynamic covalent MBH reaction based on adducts with internal H-transfer capabilities was developed. By careful tuning of the substituents, rate accelerations of retro-MBH reactions of up to four orders of magnitude could be obtained. This study thus demonstrates how efficient self-sorting of catalytic systems can be achieved through an interplay of several complex emergent functionalities.

Place, publisher, year, edition, pages
Wiley , 2021. Vol. 27, no 40, p. 10335-10340
Keywords [en]
dynamic covalent chemistry, dynamic systems, imine exchange, Morita-Baylis-Hillman reactions, organocatalysis
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-299488DOI: 10.1002/chem.202100208ISI: 000674175400015PubMedID: 33780566Scopus ID: 2-s2.0-85105174812OAI: oai:DiVA.org:kth-299488DiVA, id: diva2:1584559
Note

QC 20210812

Available from: 2021-08-12 Created: 2021-08-12 Last updated: 2022-06-25Bibliographically approved

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Schaufelberger, FredrikRamström, Olof

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