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Resolution of Dynamic Systems: Applications in Asymmetric Synthesis and Materials Science
KTH, Skolan för kemivetenskap (CHE), Kemi, Organisk kemi.
2014 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Stockholm: KTH Royal Institute of Technology, 2014. , s. 63
Serie
TRITA-CHE-Report, ISSN 1654-1081 ; 2014:34
Nationell ämneskategori
Organisk kemi
Forskningsämne
Kemi
Identifikatorer
URN: urn:nbn:se:kth:diva-151314ISBN: 978-91-7595-239-0 (tryckt)OAI: oai:DiVA.org:kth-151314DiVA, id: diva2:747955
Disputation
2014-10-10, F3, Lindstedtsvägen 26, KTH, Stockholm, 14:00 (Engelska)
Opponent
Handledare
Forskningsfinansiär
Vetenskapsrådet, KDHH B60940
Anmärkning

QC 20140918

Tillgänglig från: 2014-09-18 Skapad: 2014-09-17 Senast uppdaterad: 2022-06-23Bibliografiskt granskad
Delarbeten
1. Double parallel dynamic resolution through lipase-catalyzed asymmetric transformation
Öppna denna publikation i ny flik eller fönster >>Double parallel dynamic resolution through lipase-catalyzed asymmetric transformation
2013 (Engelska)Ingår i: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 49, nr 18, s. 1805-1807Artikel i tidskrift (Refereegranskat) 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.

Ort, förlag, år, upplaga, sidor
RSC Publishing, 2013
Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:kth:diva-119127 (URN)10.1039/c3cc38203f (DOI)000314650100006 ()23348957 (PubMedID)2-s2.0-84873606019 (Scopus ID)
Forskningsfinansiär
Vetenskapsrådet
Anmärkning

QC 20130311

Tillgänglig från: 2013-03-11 Skapad: 2013-03-07 Senast uppdaterad: 2024-03-15Bibliografiskt granskad
2. Silver-catalyzed dynamic systemic resolution of alpha-iminonitriles in a 1,3-dipolar cycloaddition process
Öppna denna publikation i ny flik eller fönster >>Silver-catalyzed dynamic systemic resolution of alpha-iminonitriles in a 1,3-dipolar cycloaddition process
2014 (Engelska)Ingår i: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 50, nr 29, s. 3792-3794Artikel i tidskrift (Refereegranskat) 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.

Nyckelord
Combinatorial Resolution, Asymmetric-Synthesis, Azomethine Ylides, Inhibitors, Alkaloids, Transformation, Indolizidine, Derivatives, Complexes, Chemistry
Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:kth:diva-144568 (URN)10.1039/c4cc00944d (DOI)000333037000005 ()24576940 (PubMedID)2-s2.0-84896268279 (Scopus ID)
Forskningsfinansiär
Vetenskapsrådet
Anmärkning

QC 20140425

Tillgänglig från: 2014-04-25 Skapad: 2014-04-24 Senast uppdaterad: 2024-03-15Bibliografiskt granskad
3. Gelation-Driven Dynamic Systemic Resolution: in situ Generation and Self-Selection of an Organogelator
Öppna denna publikation i ny flik eller fönster >>Gelation-Driven Dynamic Systemic Resolution: in situ Generation and Self-Selection of an Organogelator
(Engelska)Manuskript (preprint) (Övrigt vetenskapligt)
Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:kth:diva-151320 (URN)
Anmärkning

QS 2014

Tillgänglig från: 2014-09-18 Skapad: 2014-09-18 Senast uppdaterad: 2022-06-23Bibliografiskt granskad
4. Lipase-catalyzed asymmetric synthesis of oxathiazinanones through dynamic covalent kinetic resolution
Öppna denna publikation i ny flik eller fönster >>Lipase-catalyzed asymmetric synthesis of oxathiazinanones through dynamic covalent kinetic resolution
2014 (Engelska)Ingår i: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 12, nr 22, s. 3572-3575Artikel i tidskrift (Refereegranskat) 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.

Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:kth:diva-147756 (URN)10.1039/c4ob00365a (DOI)000336782000006 ()24759850 (PubMedID)2-s2.0-84900819904 (Scopus ID)
Forskningsfinansiär
Vetenskapsrådet
Anmärkning

QC 20140704

Tillgänglig från: 2014-07-04 Skapad: 2014-07-03 Senast uppdaterad: 2024-03-15Bibliografiskt granskad
5. Efficient asymmetric synthesis of lamivudine via enzymatic dynamic kinetic resolution
Öppna denna publikation i ny flik eller fönster >>Efficient asymmetric synthesis of lamivudine via enzymatic dynamic kinetic resolution
2013 (Engelska)Ingår i: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 49, nr 88, s. 10376-10378Artikel i tidskrift (Refereegranskat) 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.

Nyckelord
Potent Antiviral Agent, Secondary Alcohols, Enantioselective Synthesis, Nucleoside Analogs, Organic-Synthesis, Anti-Hiv, Lipase, Replication, Catalysts, 3tc(Tm)
Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:kth:diva-133666 (URN)10.1039/c3cc45551c (DOI)000325723900011 ()24071972 (PubMedID)2-s2.0-84885455365 (Scopus ID)
Forskningsfinansiär
Vetenskapsrådet
Anmärkning

QC 20131108

Tillgänglig från: 2013-11-08 Skapad: 2013-11-08 Senast uppdaterad: 2024-03-15Bibliografiskt granskad
6. Asymmetric Synthesis of Lamivudine and its Enantiomer: Mechanism of Chirality Control in Enzyme-Catalyzed 1,3-Oxathiolane Ring Closing Processes
Öppna denna publikation i ny flik eller fönster >>Asymmetric Synthesis of Lamivudine and its Enantiomer: Mechanism of Chirality Control in Enzyme-Catalyzed 1,3-Oxathiolane Ring Closing Processes
(Engelska)Manuskript (preprint) (Övrigt vetenskapligt)
Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:kth:diva-151319 (URN)
Anmärkning

QS 2014

Tillgänglig från: 2014-09-18 Skapad: 2014-09-18 Senast uppdaterad: 2022-06-23Bibliografiskt granskad

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