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Resolution of Dynamic Systems: Applications in Asymmetric Synthesis and Materials Science
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is built on the concepts of constitutional dynamic chemistry and dynamic kinetic resolution, where reversible covalent reactions are used to generate dynamics and kinetically controlled reactions are employed for resolution. The thesis is divided into two parts:

The first section focuses on the study of dynamic systemic resolution, a concept derived from constitutional dynamic chemistry. Three projects are addressed in this section: 1) lipase-catalyzed resolution of a double parallel dynamic system involving both hemiacetal formation and nitroaldol reaction; 2) resolution of a dynamic α-iminonitrile system through a silver-catalyzed 1,3-dipolar cycloaddition process; 3) resolution of a dynamic imine system via organogelation. Both external and internal selection pressures are applied for the resolution of complex dynamic systems.

The second section explores the asymmetric synthesis of two types of heterocycles through dynamic kinetic resolution. In the first example, a series of novel N-, O-, S-containing six-membered oxathiazinanones are obtained through a lipase-mediated dynamic domino nitrone addition-cyclization pathway. In the second example, the anti-HIV nucleoside lamivudine is synthesized through a three-step surfactant-treated subtilisin Carlsberg-catalyzed dynamic kinetic resolution protocol. Its enantiomer is also accessible by changing subtilisin Carlsberg to lipases. In addition, the enzyme selectivity towards the formation of five-membered oxathiolane derivatives is investigated.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. , 63 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2014:34
National Category
Organic Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-151314ISBN: 978-91-7595-239-0 (print)OAI: oai:DiVA.org:kth-151314DiVA: diva2:747955
Public defence
2014-10-10, F3, Lindstedtsvägen 26, KTH, Stockholm, 14:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council, KDHH B60940
Note

QC 20140918

Available from: 2014-09-18 Created: 2014-09-17 Last updated: 2014-09-18Bibliographically approved
List of papers
1. Double parallel dynamic resolution through lipase-catalyzed asymmetric transformation
Open this publication in new window or tab >>Double parallel dynamic resolution through lipase-catalyzed asymmetric transformation
2013 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 49, no 18, 1805-1807 p.Article in journal (Refereed) Published
Abstract [en]

Dynamic systems based on double parallel reactions have been generated and resolved in situ by secondary lipase-catalyzed asymmetric transformation, resulting in high chemo- and enantioselectivities.

Place, publisher, year, edition, pages
RSC Publishing, 2013
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-119127 (URN)10.1039/c3cc38203f (DOI)000314650100006 ()2-s2.0-84873606019 (Scopus ID)
Funder
Swedish Research Council
Note

QC 20130311

Available from: 2013-03-11 Created: 2013-03-07 Last updated: 2017-12-06Bibliographically approved
2. Silver-catalyzed dynamic systemic resolution of alpha-iminonitriles in a 1,3-dipolar cycloaddition process
Open this publication in new window or tab >>Silver-catalyzed dynamic systemic resolution of alpha-iminonitriles in a 1,3-dipolar cycloaddition process
2014 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 50, no 29, 3792-3794 p.Article in journal (Refereed) Published
Abstract [en]

A dynamic azomethine ylide system was established using Sc(OTf)(3) and Ag/Taniaphos as catalysts. The system was subsequently kinetically resolved in a tandem 1,3-dipolar cycloaddition process where the silver complex acted as both a reaction catalyst and an external selector, resulting in the formation of an exclusive pyrrolidine product in good yield and enantiopurity.

Keyword
Combinatorial Resolution, Asymmetric-Synthesis, Azomethine Ylides, Inhibitors, Alkaloids, Transformation, Indolizidine, Derivatives, Complexes, Chemistry
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-144568 (URN)10.1039/c4cc00944d (DOI)000333037000005 ()2-s2.0-84896268279 (Scopus ID)
Funder
Swedish Research Council
Note

QC 20140425

Available from: 2014-04-25 Created: 2014-04-24 Last updated: 2017-12-05Bibliographically approved
3. 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
(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-151320 (URN)
Note

QS 2014

Available from: 2014-09-18 Created: 2014-09-18 Last updated: 2014-09-18Bibliographically approved
4. Lipase-catalyzed asymmetric synthesis of oxathiazinanones through dynamic covalent kinetic resolution
Open this publication in new window or tab >>Lipase-catalyzed asymmetric synthesis of oxathiazinanones through dynamic covalent kinetic resolution
2014 (English)In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 12, no 22, 3572-3575 p.Article in journal (Refereed) Published
Abstract [en]

A domino addition-lactonization pathway has been applied to a dynamic covalent resolution protocol, leading to efficient oxathiazinanone formation as well as chiral discrimination. A new, double biocatalytic pathway has furthermore been proposed and evaluated where the initial product inhibition could be efficiently circumvented.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-147756 (URN)10.1039/c4ob00365a (DOI)000336782000006 ()2-s2.0-84900819904 (Scopus ID)
Funder
Swedish Research Council
Note

QC 20140704

Available from: 2014-07-04 Created: 2014-07-03 Last updated: 2017-12-05Bibliographically approved
5. Efficient asymmetric synthesis of lamivudine via enzymatic dynamic kinetic resolution
Open this publication in new window or tab >>Efficient asymmetric synthesis of lamivudine via enzymatic dynamic kinetic resolution
2013 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 49, no 88, 10376-10378 p.Article in journal (Refereed) Published
Abstract [en]

The anti-HIV nucleoside lamivudine was asymmetrically synthesized in only three steps via a novel surfactant-treated subtilisin Carlsberg-catalyzed dynamic kinetic resolution protocol. The enantiomer of lamivudine could also be accessed using the same protocol catalyzed by Candida antarctica lipase B.

Keyword
Potent Antiviral Agent, Secondary Alcohols, Enantioselective Synthesis, Nucleoside Analogs, Organic-Synthesis, Anti-Hiv, Lipase, Replication, Catalysts, 3tc(Tm)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-133666 (URN)10.1039/c3cc45551c (DOI)000325723900011 ()2-s2.0-84885455365 (Scopus ID)
Funder
Swedish Research Council
Note

QC 20131108

Available from: 2013-11-08 Created: 2013-11-08 Last updated: 2017-12-06Bibliographically approved
6. Asymmetric Synthesis of Lamivudine and its Enantiomer: Mechanism of Chirality Control in Enzyme-Catalyzed 1,3-Oxathiolane Ring Closing Processes
Open this publication in new window or tab >>Asymmetric Synthesis of Lamivudine and its Enantiomer: Mechanism of Chirality Control in Enzyme-Catalyzed 1,3-Oxathiolane Ring Closing Processes
(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-151319 (URN)
Note

QS 2014

Available from: 2014-09-18 Created: 2014-09-18 Last updated: 2014-09-18Bibliographically approved

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