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Kinetic Self-Sorting of Dynamic Covalent Catalysts with Systemic Feedback Regulation
KTH, School of Chemical Science and Engineering (CHE), Chemistry.ORCID iD: 0000-0001-5298-4310
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2016 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 138, no 25, 7836-7839 p.Article in journal (Refereed) Published
Resource type
Text
Abstract [en]

Constructing small molecule systems that mimic the functionality exhibited in biological reaction networks is a key objective of systems chemistry. Herein, we report the development of a dynamic catalytic system where the catalyst activity is modulated through a dynamic covalent bond. By connecting a thermodynamically controlled rearrangement process to resolution under kinetic control, the catalyst system underwent kinetic self sorting, resulting in amplification of a more reactive catalyst while establishing a catalytic feedback mechanism. The dynamic catalyst system furthermore responded to catalytic events by self-perturbation to regulate its own activity, which in the case of upregulation gave rise to systemic autocatalytic behavior.

Place, publisher, year, edition, pages
American Chemical Society , 2016. Vol. 138, no 25, 7836-7839 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-190675DOI: 10.1021/jacs.6b04250ISI: 000378984300009PubMedID: 27304874Scopus ID: 2-s2.0-84976597278OAI: oai:DiVA.org:kth-190675DiVA: diva2:953017
Note

QC 20160816

Available from: 2016-08-16 Created: 2016-08-12 Last updated: 2017-01-16Bibliographically 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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