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Synthesis and study of new oxazoline-based ligands
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis deals with the study of oxazoline-based ligands in metal-catalyzed asymmetric reactions.

The first part describes the synthesis of six new bifunctinal pyridine-bis(oxazoline) ligands and their applications in asymmetric metal-catalysis. These ligands, in addition to a Lewis acid coordination site, are equipped with a Lewis basic part in the 4-position of the oxazoline rings. Dual activation by means of this system was probed in cyanide addition to aldehydes.

The second part is concerned with the synthesis of two pyridine-bis(oxazoline) ligands bearing bulky triazole groups in the 4-position of the oxazoline rings and a macrocyclic ligand consisting of a pyridine-bis(oxazoline) moiety and a diaza-18-crown-6 ether. The synthesis of these compounds benefits from the use of “click chemistry”. The ligands thus obtained were tested in different asymmetric catalytic reactions. Complexation studies with different bifunctional molecules that could bind into the cavity of the macrocycle were carried out using NMR spectroscopy.

A third chapter is devoted to the synthesis of a supported pyridine-bis(oxazoline) catalyst and its use in catalysis. The pyridine-bis(oxazoline) ligand was efficiently connected to a polystyrene resin via a robust triazole linker. This resin could be employed in different metal-catalyzed asymmetric reactions and good results were obtained in terms of yield and enantioselectivity. Moreover, this polymer-bound ligand could be easily and efficiently recycled.

Finally, the last part deals with the use of a hydroxy-containing phosphinooxazoline ligand in the hydrosilylation of imines and in the asymmetric intermolecular Heck reaction. A cationic iridium complex of this ligand was studied by NMR spectroscopy.

Place, publisher, year, edition, pages
Stockholm: KTH , 2008. , 101 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:54
Keyword [en]
organic chemistry
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-4858ISBN: 978-91-7415-093-3 (print)OAI: oai:DiVA.org:kth-4858DiVA: diva2:94
Public defence
2008-09-19, E3, Osquars Backe 14, KTH, 10:00 (English)
Opponent
Supervisors
Note
QC 20100914Available from: 2008-09-10 Created: 2008-09-04 Last updated: 2010-09-14Bibliographically approved
List of papers
1. Polymer-Bound Pyridine-Bis(oxazoline). Preparation through Click Chemistry and Evaluation in Asymmetric Catalysis
Open this publication in new window or tab >>Polymer-Bound Pyridine-Bis(oxazoline). Preparation through Click Chemistry and Evaluation in Asymmetric Catalysis
2007 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 349, no 13, 2079-2084 p.Article in journal (Refereed) Published
Abstract [en]

A pyridine-bis(oxazoline) ligand was efficiently immobilized by copper(I)-catalyzed azide-alkyne cycloaddition onto a polystyrene resin. The so obtained click-pybox resin 1a was associated with various metal salts (YbCl3, LuCl3, CuOTf) and the resulting resin-bound catalysts were explored in ring-opening of cyclohexene oxide, silylcyanation of benzaldehyde and alkynylation of imines. These new polymer-supported catalysts exhibit good to excellent performances in terms of catalytic activity, enantioselectivity and recyclability.

Keyword
asymmetric catalysis, click chemistry, copper(I), immobilization, lanthanides, pybox
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-4886 (URN)10.1002/adsc.200700112 (DOI)000249833300001 ()2-s2.0-34948850749 (Scopus ID)
Note
QC 20100914Available from: 2008-09-16 Created: 2008-09-16 Last updated: 2017-12-13Bibliographically approved
2. Convenient Preparation of Bifunctional Pybox Ligands
Open this publication in new window or tab >>Convenient Preparation of Bifunctional Pybox Ligands
2008 (English)In: Tetrahedron: asymmetry, ISSN 0957-4166, E-ISSN 1362-511X, Vol. 64, no 44, 10244-10249 p.Article in journal (Refereed) Published
Abstract [en]

 Starting from a common easily available pybox derivative, chiral ditopic ligands with pendant Lewis basic sites consisting of amine or phosphine oxide functions attached in the 4-positions of the oxazoline rings were prepared by simple synthetic procedures. From the same pybox derivative, a macrocyclic ligand containing a diaza-18-crown-6-ether ring linked via triazole groups was obtained employing 'click' chemistry.

Keyword
CATALYZED ALLYLIC SUBSTITUTION, ASYMMETRIC CATALYSIS, CHIRAL LIGANDS, LEWIS-ACID, BIS(OXAZOLINE) LIGANDS, ALPHA-KETOESTERS, COMPLEXES, ENANTIOSELECTIVITY, ALKYLATION, CYCLOPROPANATION
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-4887 (URN)10.1016/j.tet.2008.08.016 (DOI)000260290500017 ()2-s2.0-51349106137 (Scopus ID)
Note
QC 20100906. Uppdaterad från Accepted till Published (20100906)Available from: 2008-09-16 Created: 2008-09-16 Last updated: 2017-12-13Bibliographically approved
3. Influence of Ligand Secondary Interactions on Dynamic Processes in Alkene Ir Complexes
Open this publication in new window or tab >>Influence of Ligand Secondary Interactions on Dynamic Processes in Alkene Ir Complexes
Show others...
(English)Manuscript (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-4888 (URN)
Note
QC 20100914Available from: 2008-09-16 Created: 2008-09-16 Last updated: 2010-09-14Bibliographically approved
4. Evaluation of new pyridine-bis(oxazoline) ligands in asymmetric catalysis
Open this publication in new window or tab >>Evaluation of new pyridine-bis(oxazoline) ligands in asymmetric catalysis
Show others...
(English)Manuscript (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-4889 (URN)
Note
QC 20100914Available from: 2008-09-16 Created: 2008-09-16 Last updated: 2010-09-14Bibliographically approved

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