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Synthesis of Novel Chiral Bicyclic Ligands and their Application in Iridium-Catalyzed Reactions
Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The synthesis of 2-aza-norborane derivatives is presented. The use of these compounds in preparation of Ir catalysts for asymmetric hydrogenations is described. The evaluation and optimization of the catalysts as well as the mechanistic aspects of the catalytic process are discussed.

The use of non-activated iminodieniphiles in stereoselective aza-Diels-Alder reaction has expanded the scope of the reaction and provided a convenient root for preparation of 2-aza-norboranes, analogues of which were developed into novel bicyclic 2-aza-norbornyl-oxazoline ligands for Ir-catalyzed asymmetric transfer hydrogenations. Using ths Ir complexes acetophenone was hydrogenated in 79% ee.

2-Aza-norbornyl-oxazolines were also developed into novel N,P-ligands. Resulting phosphine-oxazolines were evaluated in Ir-catalyzed asymmetric hydrogenation of structurally diverse imines and olefins.

Optimization of ligands was performed through: 1) Alteration of the stereoconfiguration at the 5’-position as well as variation of the size and geometry of the substituents at this position; 2) Screening through various phosphine substituents of the ligand. Both directions of optimization reflect on the influence of the ligands’ sterik bulk on stereoselectivity of catalytic process. High performance catalysts were developed for both transformations allowing asymmetric hydrogenation of imines with 92% ee and asymmetric hydrogenation of olefins with 99% ee.

Possible mechanisms for these transformations were suggested based on computational studies. Selectivity model for rationalization of results of Ir-catalyzed olefin hydrogenation also was designed.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis , 2005. , p. 72
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 50
Keywords [en]
Organic chemistry, asymmetric catalysis, Diels-Alder reaction, transfer hydrogenation, hydrogenation, amino-oxazoline, phosphine-oxazoline, imine, olefin
Keywords [sv]
Organisk kemi
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-5783ISBN: 91-554-6243-X (print)OAI: oai:DiVA.org:uu-5783DiVA, id: diva2:166374
Public defence
2005-05-28, Room B42, BMC, Husargatan 3, Uppsala, 10:15
Opponent
Supervisors
Available from: 2005-05-04 Created: 2005-05-04Bibliographically approved
List of papers
1. The use of nonactivated iminodienophiles in the stereoselective aza-Diels-Alder reaction
Open this publication in new window or tab >>The use of nonactivated iminodienophiles in the stereoselective aza-Diels-Alder reaction
2004 In: Tetrahedron: Asymmetry, ISSN 0957-4166, Vol. 15, no 3, p. 445-452Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-93021 (URN)
Available from: 2005-05-04 Created: 2005-05-04Bibliographically approved
2. Development of a new class of (1S,3R,4R)-2-azabicyclo[2.2.1]heptane-oxazoline ligands and their application in asymmetric transfer hydrogenation
Open this publication in new window or tab >>Development of a new class of (1S,3R,4R)-2-azabicyclo[2.2.1]heptane-oxazoline ligands and their application in asymmetric transfer hydrogenation
2004 In: Tetrahedron, ISSN 0040-4020, Vol. 60, no 15, p. 3393-3403Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-93022 (URN)
Available from: 2005-05-04 Created: 2005-05-04Bibliographically approved
3. Application of Phosphine-Oxazoline Ligands in Ir-Catalyzed Asymmetric Hydrogenation of Acyclic Aromatic N-Arylimines
Open this publication in new window or tab >>Application of Phosphine-Oxazoline Ligands in Ir-Catalyzed Asymmetric Hydrogenation of Acyclic Aromatic N-Arylimines
2004 In: Organic Letters, ISSN 1523-7060, Vol. 6, no 21, p. 3825-3837Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-93023 (URN)
Available from: 2005-05-04 Created: 2005-05-04Bibliographically approved
4. Asymmetric Hydrogenation of Imines and Olefins Using Phosphine-oxazoline Iridium Complexes as Catalysts
Open this publication in new window or tab >>Asymmetric Hydrogenation of Imines and Olefins Using Phosphine-oxazoline Iridium Complexes as Catalysts
Manuscript (Other academic)
Identifiers
urn:nbn:se:uu:diva-93024 (URN)
Available from: 2005-05-04 Created: 2005-05-04 Last updated: 2010-01-13Bibliographically approved

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