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Development of highly modular ligands for use in asymmetric transition-metal catalyzed reactions
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The synthesis and evaluation of ligands for use in asymmetric transition metal catalyzed reactions is a widely used concept to achieve improved enantioselectivity in a variety of different transformations. The present thesis decribes the synthesis of a number of different oxazoline-based ligands and their use in titanum-catalyzed addition of diethyl zinc to aliphatic and aromatic aldehydes. Interestingly, the presence of catalytic amounts of titanium in our system was sufficient to achieve effective catalysis in contrast to what has been previously reported concerning titanium-catalyzed addition of diethyl zinc to aldehydes.

The synthesis and evaluation of a library of novel dipeptide-like ligands are described and these ligands were employed in connection with ruthenium-catalyzed transfer hydrogenation of aromatic ketones. Excellent enantioselectivities and yields were obtained.

Furthermore, the novel concept of forming the ligand and catalyst in situ in a one-pot system was explored. In addition to significant simplification, this approach resulted in improvements in both enantioselectivity (minor) and reaction rate (2-3 fold) compared to previously studied procedures.

The surprizing influence of alkali salts on ruthenium-catalyzed transfer hydrogenation involving these dipeptide-like ligands are described and discussed. In the presence of these additives the ruthenium-catalyzed transfer hydrogenation performed with higher enantioselecitvity and reactivity.

Finally, mechanistic studies concerning ruthenium-catalyzed transfer hydrogenation involving the dipeptide-like ligands are also described and discussed.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi , 2005. , 51 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-454ISBN: 91-7155-055-0 (print)OAI: oai:DiVA.org:su-454DiVA: diva2:194098
Public defence
2005-05-04, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00
Opponent
Supervisors
Available from: 2005-04-13 Created: 2005-04-13Bibliographically approved
List of papers
1. 2-(Aminomethyl)-oxazolines: Highly modular scaffold for the preparation of novel asymmetric ligands
Open this publication in new window or tab >>2-(Aminomethyl)-oxazolines: Highly modular scaffold for the preparation of novel asymmetric ligands
2005 In: Journal of Organic Chemistry, Vol. 70, no 8, 2921-2929 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23711 (URN)
Note
Part of urn:nbn:se:su:diva-454Available from: 2005-04-13 Created: 2005-04-13Bibliographically approved
2. Novel simple and highly modular ligands for the efficient asymmetric transfer-hydrogenation of ketones
Open this publication in new window or tab >>Novel simple and highly modular ligands for the efficient asymmetric transfer-hydrogenation of ketones
2002 In: Chemical Communications, ISSN 1359-7345, no 18, 2046-2047 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23712 (URN)
Note
Part of urn:nbn:se:su:diva-454Available from: 2005-04-13 Created: 2005-04-13Bibliographically approved
3. Employing the structural diversity of nature: Development of modular dipeptide-analogue ligands for ruthenium-catalyzed enantioselective transfer-hydrogenation of ketones
Open this publication in new window or tab >>Employing the structural diversity of nature: Development of modular dipeptide-analogue ligands for ruthenium-catalyzed enantioselective transfer-hydrogenation of ketones
2003 In: Chemistry a European journal, ISSN 1521-3765, Vol. 9, no 17, 4031-4045 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23713 (URN)
Note
Part of urn:nbn:se:su:diva-454Available from: 2005-04-13 Created: 2005-04-13Bibliographically approved
4. Ruthenium-catalyzed enantioselective reduction of ketones - in situ formation of ligand and catalyst
Open this publication in new window or tab >>Ruthenium-catalyzed enantioselective reduction of ketones - in situ formation of ligand and catalyst
Manuscript (Other academic)
Identifiers
urn:nbn:se:su:diva-23714 (URN)
Note
Part of urn:nbn:se:su:diva-454Available from: 2005-04-13 Created: 2005-04-13 Last updated: 2010-01-13Bibliographically approved
5. The importance of alkali cations in the ruthenium-catalyzed enantioselective transfer-hydrogenation of ketones - novel mechanistic implications
Open this publication in new window or tab >>The importance of alkali cations in the ruthenium-catalyzed enantioselective transfer-hydrogenation of ketones - novel mechanistic implications
Manuscript (Other academic)
Identifiers
urn:nbn:se:su:diva-23715 (URN)
Note
Part of urn:nbn:se:su:diva-454Available from: 2005-04-13 Created: 2005-04-13 Last updated: 2010-01-13Bibliographically approved

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