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Trans-Symmetric Dynamic Covalent Systems: Connected Transamination and Transimination Reactions
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0001-5298-4310
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2015 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 21, no 27, 9776-9783 p.Article in journal (Refereed) Published
Abstract [en]

The development of chemical transaminations as a new type of dynamic covalent reaction is described. The key 1,3-proton shift is under complete catalytic control and can be conducted orthogonally to, or simultaneous with, transimination in the presence of an amine to rapidly yield two-dimensional dynamic systems with a high degree of complexity evolution. The transamination-transimination systems are proven to be fully reversible, stable over several days, compatible with a range of functional groups, and highly tunable. Kinetic studies show transamination to be the rate-limiting reaction in the network. Furthermore, it was discovered that readily available quinuclidine is a highly potent catalyst for aldimine transaminations. This study demonstrates how connected dynamic reactions give rise to significantly larger systems than the unconnected counterparts, and shows how reversible isomerizations can be utilized as an effective diversity-generating element.

Place, publisher, year, edition, pages
2015. Vol. 21, no 27, 9776-9783 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-171289DOI: 10.1002/chem.201500520ISI: 000357027300027PubMedID: 26044061Scopus ID: 2-s2.0-84934980702OAI: oai:DiVA.org:kth-171289DiVA: diva2:843237
Note

QC 20150728

Available from: 2015-07-28 Created: 2015-07-27 Last updated: 2017-12-04Bibliographically approved
In thesis
1. Catalysis in Dynamic Systems: Control within Molecular Reaction Networks
Open this publication in new window or tab >>Catalysis in Dynamic Systems: Control within Molecular Reaction Networks
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Life as we know it is based on complex networks of biochemical reactions that constantly interact within large dynamic systems. The field of systems chemistry uses chemical models to study how reaction networks – and thereby life – function on a molecular level. This thesis focuses on different aspects of catalysis in dynamic systems of interconnected reversible reactions. Using the reversible imine bond as the primary tool, such dynamic systems have both been used for catalyst screening and to achieve emergent systemic behavior.

First, constitutional dynamic chemistry was used to discover catalysts within large mixtures. A method based on dynamic deconvolution was used to identify a bifunctional organocatalyst for the Morita-Baylis-Hillman (MBH) reaction from a mixture of 16 candidates. A second method involved amplification of an organometallic intermediate from a dynamic system and was used to discover directing group/metal combinations for C-H functionalization of aldehydes.

Subsequently, the consequences of integrating the catalyst itself into a dynamic system were investigated. Here, dynamic covalent catalysts formed reaction networks with programmable systemic properties. Using the MBH reaction and dynamic imine exchange, catalysts capable of self-resolution, feedback regulation and error-correction were constructed.

Finally, selective catalyst systems for activation of new reversible covalent behavior for imines were developed. H-bond catalysis was used to facilitate imine exchange under mild conditions, and transamination was introduced as a dynamic covalent linkage that could change the directionality of the imine bond.

The research in this thesis should both be applicable for catalyst discovery within synthetic organic chemistry, for understanding connectivity in chemical and biological systems as well as for studies of the origin of life on earth and the evolution of simple molecules into advanced systems with emergent functionality.

Place, publisher, year, edition, pages
Stockholm: Kungliga Tekniska högskolan, 2017. 90 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2017:7
Keyword
systems chemistry, dynamic covalent chemistry, catalyst screening, reaction networks, organocatalysis, imine exchange, combinatorial chemistry, dynamic systemic resolution, feedback, error-correction, Morita-Baylis-Hillman reaction, C-H activation, H-bond catalysis, transamination
National Category
Organic Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-199708 (URN)978-91-7729-255-5 (ISBN)
Public defence
2017-02-17, F3, Lindstedtsvägen 26, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

QC 20170216

Available from: 2017-01-16 Created: 2017-01-15 Last updated: 2017-01-27Bibliographically approved

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Schaufelberger, Fredrik

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