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Dynamic Systems: Enzymatic Synthesis, Exchange Reactions and Applications in Materials Science
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is divided into three parts, revolving around the developments of dynamic systems utilized in dynamic kinetic resolution (DKR) and constitutional dynamic chemistry (CDC).

The first section gives an introduction to constitutional dynamics, the core concept of this thesis. Constitutional dynamics can be tuned through reversible interactions. Then, the basic principles of constitutional dynamics in DKR and CDC are discussed, along with their applications.

The second section explores the asymmetric synthesis of oxazolidinone derivatives using lipase catalysis through kinetic resolution (KR) and dynamic kinetic resolution. In the first example, synthetic protocol to enantioenriched 5-phenyloxazolidin-2-ones is described, where a kinetically controlled carbamation is followed by lipase-catalyzed cyclization. In contrast to the 5-substituted species, the synthesis of 3-phenyloxazolidin-2-one derivatives could be achieved through lipase-catalyzed cascade O- and N- alkoxycarbonylations in one pot. Furthermore, this KR system could be coupled to a ruthenium-catalyzed racemization process of 1,2-aminoalcohols, thus providing an efficient DKR methodology for asymmetric transformations.

The third section focuses on dynamic systems built through reversible covalent reactions. In the first example, a selective gelation process is described, and employed to resolve dynamic imine systems consisting of gelator candidates.  In the second example, reversible reactions with aldehyde enamines are presented, including enamine formation and exchange reactions. In particular, Bi(III) and Sc(III) were discovered to accelerate the enamine exchange reactions by 50-400 times, in which the equilibria could be reached within hours. The last example describes reversible nitroaldol reactions in aqueous media, where rapid and efficient equilibration was identified for selected structures in neutral phosphate buffer.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. , 66 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:36
Keyword [en]
constitutional dynamic chemistry, reversible reactions, kinetic resolution, dynamic kinetic resolution, enzyme catalysis, lipase, asymmetric synthesis, racemization, oxazolidinone, organogel, enamine, nitroaldol reaction.
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:kth:diva-173480ISBN: 978-91-7595-644-2 (print)OAI: oai:DiVA.org:kth-173480DiVA: diva2:853142
Public defence
2015-10-01, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20150911

Available from: 2015-09-11 Created: 2015-09-11 Last updated: 2015-09-11Bibliographically approved
List of papers
1. Synthesis of chiral oxazolidinone derivatives through lipase-catalyzed kinetic resolution
Open this publication in new window or tab >>Synthesis of chiral oxazolidinone derivatives through lipase-catalyzed kinetic resolution
2015 (English)In: Journal of Molecular Catalysis B: Enzymatic, ISSN 1381-1177, E-ISSN 1873-3158, Vol. 122, 29-34 p.Article in journal (Refereed) Published
Abstract [en]

The synthesis of enantioenriched oxazolidinone derivatives through lipase-catalyzed kinetic resolution is described. The synthesis comprised a two-step, cascade acylation in one pot, resulting in a range of oxazolidinone derivatives in good yields and excellent enantiopurities.

Keyword
Catalysis, Lipases, Asymmetric synthesis, Kinetic resolution, Lipase-catalyzed, One pot, Oxazolidinones, Kinetics
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-173481 (URN)10.1016/j.molcatb.2015.08.004 (DOI)000366078800004 ()2-s2.0-84940780895 (Scopus ID)
Note

QC 20150911

Available from: 2015-09-11 Created: 2015-09-11 Last updated: 2017-12-04Bibliographically approved
2. Lipase-Catalyzed Kinetic Resolution of 3-Phenyloxazolidin-2-one Derivatives: CascadeO‐ and N‐Alkoxycarbonylations
Open this publication in new window or tab >>Lipase-Catalyzed Kinetic Resolution of 3-Phenyloxazolidin-2-one Derivatives: CascadeO‐ and N‐Alkoxycarbonylations
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-173484 (URN)
Note

QS 2015

Available from: 2015-09-11 Created: 2015-09-11 Last updated: 2015-09-11Bibliographically approved
3. Enzyme- and Ruthenium-Catalyzed Dynamic Kinetic Resolution Involving Cascade Alkoxycarbonylations for Asymmetric Synthesis of 5-Substituted N-Aryloxazolidinones
Open this publication in new window or tab >>Enzyme- and Ruthenium-Catalyzed Dynamic Kinetic Resolution Involving Cascade Alkoxycarbonylations for Asymmetric Synthesis of 5-Substituted N-Aryloxazolidinones
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-173486 (URN)
Note

QS 2015

Available from: 2015-09-11 Created: 2015-09-11 Last updated: 2015-09-11Bibliographically approved
4. Gelation-driven Dynamic Systemic Resolution: in situ Generation and Self-Selection of an Organogelator
Open this publication in new window or tab >>Gelation-driven Dynamic Systemic Resolution: in situ Generation and Self-Selection of an Organogelator
2015 (English)In: Scientific Reports, ISSN 2045-2322, E-ISSN 2045-2322, Vol. 5, 11065Article in journal (Refereed) Published
Abstract [en]

An organogelator was produced and identified from a dynamic imine system, resolved and amplified by selective gelation. The formation of the organogel was monitored in situ by H-1 NMR, showing the existence of multiple reversible reactions operating simultaneously, and the redistribution of the involved species during gelation. The formed organogelator proved effective with a range of organic solvents, including DMSO, toluene, and longer, linear alcohols.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-170970 (URN)10.1038/srep11065 (DOI)000356513900001 ()26062041 (PubMedID)
Note

QC 20150713

Available from: 2015-07-13 Created: 2015-07-13 Last updated: 2017-12-04Bibliographically approved
5. Dynamic Covalent Chemistry of Aldehyde Enamines: Bi(III) and Sc(III) catalysis of amine-enamine exchange
Open this publication in new window or tab >>Dynamic Covalent Chemistry of Aldehyde Enamines: Bi(III) and Sc(III) catalysis of amine-enamine exchange
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-173488 (URN)
Note

QS 2015

Available from: 2015-09-11 Created: 2015-09-11 Last updated: 2015-09-11Bibliographically approved
6. Kinetics and Thermodynamics of Dynamic Nitroaldol Systems in Neutral Aqueous Media
Open this publication in new window or tab >>Kinetics and Thermodynamics of Dynamic Nitroaldol Systems in Neutral Aqueous Media
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-173489 (URN)
Note

QS 2015

Available from: 2015-09-11 Created: 2015-09-11 Last updated: 2015-09-11Bibliographically approved

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