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Metals in Dynamic Chemistry: Selection & Catalysis
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In the adaptation to the oxidative environment on earth, metals played a crucial role for the evolution of life. The presence of metals also allowed access to advanced functions due to their unique coordination sphere and reactivity. This thesis focused on exploiting these unique properties for further development of the field of dynamic chemistry – a field in which adaptation plays a central role as well.

The first part of the thesis aimed to create a better understanding of multivalent effects in carbohydrate-lectin interactions. By reversible ligand coordination to zinc ions one of the nanoplatforms, the Borromean rings, could be selectively obtained. After carbohydrate functionalization the binding events were monitored by quartz crystal microbalance technology and compared to glycosylated fullerenes and dodecaamide cages. Overall, this investigation indicated that statistical and polyelectrolyte effects play a considerable role in the observed multivalent effects.

The second part of the thesis aimed to design and synthesize a new catalyst for application in aqueous olefin metathesis. This afforded a ruthenium based catalyst that was applied in the self- and cross-metathesis of highly functionalized substrates, such as carbohydrates. In addition, it was shown that addition of a small amount of acetic acid prevented undesired double bond isomerization.

The last part of the thesis aimed to explore new methods to discover transition metal catalysts. Dynamic exchange of directing groups generated a pool of potential substrates for C-H activation. Combining this pool of substrates with a pool of potential catalysts resulted in amplification of a reactive substrate/metal combination. By iterative deconvolution in combination with mass spectrometry, this “intermediate” could be identified from the mixture, proving applicability of this alternative approach to catalyst discovery.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2017. , p. 71
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2017:32
Keywords [en]
constitutional dynamic chemistry, selection, multivalent interactions, carbohydrates, quartz crystal microbalance, catalyst screening, aqueous olefin metathesis, C-H activation
National Category
Organic Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-211492ISBN: 978-91-7729-470-2 (print)OAI: oai:DiVA.org:kth-211492DiVA, id: diva2:1129737
Public defence
2017-09-08, Sal F3, Lindstedtsvägen 26, Stockholm, 09:00 (English)
Opponent
Supervisors
Funder
EU, FP7, Seventh Framework Programme, 289033
Note

QC 20170809

Available from: 2017-08-09 Created: 2017-08-07 Last updated: 2017-08-18Bibliographically approved
List of papers
1. Spatially well-defined carbohydrate nanoplatforms: synthesis, characterization and lectin interaction study
Open this publication in new window or tab >>Spatially well-defined carbohydrate nanoplatforms: synthesis, characterization and lectin interaction study
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2016 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 52, no 83, p. 12326-12329Article in journal (Refereed) Published
Abstract [en]

Two novel dodecasubstituted carbohydrate nanoplatforms based on molecular Borromean rings and dodecaamine cages have been prepared for use in evaluating the importance of the spatial distribution of carbohydrates in their interaction with lectins. The binding affinities of the glyconanoplatforms were characterized using quartz crystal microbalance technology and compared with a monovalent reference and dodecaglycosylated fullerenes.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-196106 (URN)10.1039/c6cc06737a (DOI)000385166800014 ()27711353 (PubMedID)2-s2.0-84991489162 (Scopus ID)
Note

QC 20161111

Available from: 2016-11-11 Created: 2016-11-11 Last updated: 2017-08-07Bibliographically approved
2. Key Factors for Multivalency Effects in Carbohydrate Nanoplatform-Lectin Interactions
Open this publication in new window or tab >>Key Factors for Multivalency Effects in Carbohydrate Nanoplatform-Lectin Interactions
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(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-211488 (URN)
Funder
EU, FP7, Seventh Framework Programme, 289033
Note

QC 20170809

Available from: 2017-08-07 Created: 2017-08-07 Last updated: 2017-08-09Bibliographically approved
3. Acid-Assisted Direct Olefin Metathesis of Unprotected Carbohydrates in Water
Open this publication in new window or tab >>Acid-Assisted Direct Olefin Metathesis of Unprotected Carbohydrates in Water
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-211485 (URN)
Funder
EU, FP7, Seventh Framework Programme, 289033Swedish Research Council
Note

QC 20170803

Available from: 2017-08-03 Created: 2017-08-03 Last updated: 2017-08-09Bibliographically approved
4. Selective Cross Metathesis of Highly Functionalized Substrates in Aqueous Media
Open this publication in new window or tab >>Selective Cross Metathesis of Highly Functionalized Substrates in Aqueous Media
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-211490 (URN)
Funder
EU, FP7, Seventh Framework Programme, 289033Swedish Research Council
Note

QC 20170809

Available from: 2017-08-07 Created: 2017-08-07 Last updated: 2017-08-09Bibliographically approved
5. Resolving a Reactive Organometallic Intermediate from Dynamic Directing Group Systems by Selective C-H Activation
Open this publication in new window or tab >>Resolving a Reactive Organometallic Intermediate from Dynamic Directing Group Systems by Selective C-H Activation
(English)Manuscript (preprint) (Other academic)
Abstract [en]

Catalyst discovery from systems of potential precursors is a challenging endeavor. Herein, a new strategy applying dynamic chemistry to the identification of catalyst precursors from C-H activation of imines is proposed and evaluated. Using hydroacylation of imines as a model reaction, the selection of an organometallic reactive intermediate from a dynamic imine system, involving many potential directing group/metal entities, is demonstrated. The identity of the amplified reaction intermediate with the best directing group could be resolved in situ via ESI-MS, and coupling of the procedure to an iterative deconvolution protocol generated a system with high screening efficiency.

Keywords
Dynamic chemistry, C-H activation, Catalysis, Directing group, Systems chemistry
National Category
Organic Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-199715 (URN)
Funder
EU, FP7, Seventh Framework Programme, 289033Swedish Research Council
Note

QC 20170116

Available from: 2017-01-16 Created: 2017-01-16 Last updated: 2017-08-07Bibliographically approved

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