Christina Moberg, KTH Chemistry
Asymmetric Metal Catalysis
In this project new types of chiral ligands, in solution and bound to polymeric supports, and their metal complexes are designed and prepared for application in selective organic synthesis. In addition to the electronic and steric properties of the complexes, the role of symmetry is investigated. For this purpose ligands with pseudo-C2 and pseudo Cs symmetry have been prepared and evaluated in palladium-catalyzed allylic alkylations.
We have found that the interaction of a hydroxy group with metals in low oxidation states may play a crucial role for the stereochemistry of catalytic reactions. We have recently also initiated investigations of the addition of B-Si and Si-Si compounds to conjugated dienes with the aim to obtain chiral building blocks versatile for organic synthesis.
PhD students:
Raivis Zalubovskis
Anders Frölander
Martin Gerdin
Some recent publications:
R. Stranne and C. Moberg, “Pyrrolidinopyridines in Palladium-Catalyzed
Allylic Substitutions – Conformation of the Ligand”, Eur.
J. Org. Chem., 2001, 2191.
K. Hallman and C. Moberg, “Polymer-bound Bis(oxazoline) as a Chiral Catalyst”, Tetrahedron: Asymmetry, 2001, 12,1475.
J.-L. Vasse, R. Stranne, R. Zalubovskis, C. Gayet and C. Moberg, “The Influence of Steric Symmetry and Electronic Dissymmetry on the Enantioselectivity in Palladium Catalyzed Allylic Substitutions”, J. Org. Chem. 2003, 68, 3258.
I. Beletskaya and C. Moberg, “Element-Element Addition to Alkynes Catalyzed by the Group 10 Metals”, Chem. Rev. 1999, 99, 3435
Funding:
The Swedish Research Council
The Göran Gustafsson Foundation for Research in Sciences and Medicine
Pyridylamides in Asymmetric Catalysis
– Microwave Heating to Accelerate Catalytic Processes
Chiral pyridylamides have proven to serve as highly versatile ligands in asymmetric catalysis. We employ titanium and zirconium complexes of such ligands in Lewis acid catalyzed processes and molybdenum complexes for the enantioselective and
regioselective alkylation of allylic carbonates. The methodology was recently applied to the synthesis of the pharmaceutical (R)-baclofen.
PhD student:
Oscar Belda
Some recent publications:
O. Belda, N.-F. Kaiser, U. Bremberg, M. Larhed, A. Hallberg and C. Moberg
“Electronic and Steric Effects in Allylations Catalyzed by Mo-Pyridylamide
Complexes”, J. Org. Chem., 2000, 65,
5868.
N.-F. K. Kaiser, U. Bremberg, M. Larhed, C. Moberg and A. Hallberg, “Fast, Convenient and Efficient Molybdenum-Catalyzed Asymmetric Allylic Alkylation under Non-Inert Conditions; An Example of Microwave Promoted Fast Chemistry”, Angew. Chem. Int. Ed. Engl. 2000, 39, 3595.
O. Belda and C. Moberg, “Substituted Pyridylamide Ligands in Microwave Accelerated Mo(0) Catalysed Allylic Alkylations”, Synthesis 2002, 1601.
O. Belda, S. Lundgren and C. Moberg, “Recoverable Resin-Supported Pyridylamide Ligand for Microwave-Accelerated Molybdenum-Catalyzed Asymmetric Alkylations. Enantioselective Synthesis of Baclofen”, Org. Lett. 2003, 5, 2275.
Funding:
The Swedish Foundation for Strategic Research
New Tools for Asymmetric Catalysis - Downsizing
For the development of new catalysts and for the optimization of reaction conditions, high throughput screening is commonly used today. In collaboration with prof Göran Stemme and dr Helene Andersson and co-workers at S3, KTH, and with prof
Stephen Haswell at Hull University, we are investigating methods for downsizing of catalytic reactions. Together with the KTH team we have for example developed a method based on microcontact printing for the attachment of chiral ligands to planar and structured silicon surfaces.
PhD students:
Christina Jönsson
Stina Lundgren
Some recent publications:
H. Andersson, C. Jönsson, C. Moberg and Göran Stemme, “Consecutive
Microcontact Printing - Ligands for Asymmetric Catalysis in Silicon Channels”;
Accepted for publication in Sensors and Actuators B, 2001,
79, 78.
H. Andersson, C. Jönsson, C. Moberg and G. Stemme, “Patterened Self-Assembled Beads in Silicon Channels”, Electrophoresis 2001, 22, 3876.
H. Andersson, C. Jönsson, C. Moberg and Göran Stemme, “Self-Assembled and Self-Sorted Array of Chemically Active Beads for Analytical and Biochemical Screening”, Talanta 2002, 56, 301.
C. Jönsson, K. Hallman, H. Andersson, G. Stemme, M. Malkoch, E. Malmström, A. Hult and C. Moberg, “Immobilized Oxazoline-Containing Ligands in Asymmetric Catalysis”, Bioorg. Med. Lett., 2002, 12, 1857.
S. Lundgren, S. Lutsenko, C. Jönsson and C. Moberg, “Polymer-Supported Pyridine-bis(oxazoline). Application to Ytterbium Catalyzed Silylcyanation of Benzaldehyde, Org. Lett. 2003, 5, 3663.
Funding:
The Swedish Foundation for Strategic Research
High Symmetry Chiral Ligands
Rotational axes is the only symmetry element which is compatible with chirality. The presence of such axes in catalytically active metal complexes may play a beneficial role for the selectivity in catalytic processes.
Our studies of such high symmetry chiral catalysts are part of a European collaboration (RTN project) with groups in Italy, France, Spain, and Britain.
Postdoc:
Yuxin Pei
Some recent publications:
F. Lake, L. Hagberg, M. Svensson and C. Moberg, C3-Symmetric Azaphosphatranes
Collection of Czechoslvak Chemical Communications. 2000,
65, 570.
Funding:
EU
Palladium-Catalyzed Oxidation of Alcohols
In this project the use of palladium complexes for the catalytic oxidation of primary and secondary alcohols to aldehydes and ketones, respectively, are studied. Air is used as the oxidant in the catalytic process. Such oxidations are commonly performed with environmentally harmful metal complexes.
Postdoc:
Sari Paavola
Recent publication:
K. Hallman and C. Moberg, Palladium(II)-Catalyzed Oxidation of Alcohols with
Air as Reoxidant”, Advanced Syntehsis and Catalysis, 2001,
343, 260.
Funding:
The Göran Gustafsson Foundation for Research in Sciences and Medicine
Former group members:
PhD students:
Björn Elman 1982-86 ("The Preparation and Properties of Some 2,2´-Dipyridylmethanes" , Thesis 1986)
Thomas Antonsson 1983-88 ("New Synthetic Methods Based on Palladium-Catalyzed Transformations of Dienes", Thesis 1988)
László Rákos 1985-91 (Polymer-Supported Organic Reagents - Preparation and Aplications in Organic Synthesis, Chromatography and Hydrometallurgy", Thesis 1991)
Louise Tottie 1986-92 (“Selective Palladium-Catalyzed ransformations of 1,5-Dienes. Use of Derivatives of (R)-Lactic Acid for Asymetric Synthesis and Analysis of Chiral Compounds”, Thesis 1992)
Kenneth Wärnmark 1988-1994 (“Chiral Macrocyclic and C3-Symmetric Pyridine Ligands for Potential Use in Catalytic Asymetric Synthesis”, Thesis 1994)
Hans Adolfsson 1989-1995 (“Ligand Design for Selective Catalysis”, Thesis 1995)
Kerstin Nordström 1988-1996 (“Palladium-Catalysed Asymmetric Transformations”, Thesis 1996)
Magnus Cernerud 1992-1997 (“Versatile Ligands for Selective Metal Catalysis”, Thesis 1997)
Emmanuel Macedo 1995-1998 (“Oxazoline-Containing Ligands. Synthesis and Applications”, Thesis 1998)
Ulf Bremberg 1995-2000 (“Asymmetric Catalysis: Ligand Design and Microwave Acceleration”, Thesis 2000)
Robert Stranne 1997-2002 (“Investigation of Symmetry and Electronic Efects in Asymmetric Palladium-Catalyzed Allylic Substitutions”, Thesis 2002)
Fredrik Lake 1997-2002 (“C2- and C3-Symmetric Ligands via Ring-Opening of Aziridines: Application in Asymmetric Catalysis”, Thesis 2002)
Kristina Hallman 1998-2001 (“Asymmetric Catalysis: Ligand Design and Conformational Studies”, Thesis 2001)
Fredrik Rahm 1998-2003 (“Chiral Pyridine-Containing Ligands for Asymmetric Catalysis: Synthesis and Applications”, Thesis 2003)
Postdocs:
Lori Sutin, Canada,
post-doc 1988-91
Vincent Levacher, France, post-doc 1992-93
Simon Dunne, Australia, post-doc 1997-98
Lars Hagberg, Sweden, postdoc
Serghey Lutsenko, Russia, postdoc 1999-2003
Jean-Luc Vasse, post-doc 2000-2001
Tebikie Wondimagegn, postdoc 2001-2002
Olivier Temmem, post-doc 2001-2002
Dean Gillings, postdoc 2002-2003
Sara Paavola, postdoc 2002-
Yuxin Pei, postdoc 2003-
Diploma students:
Maria Hultenheim
1981
Louise Tottie 1985
Abraham Langlet 1986
Kenneth Wärnmark 1987
Lars Öhrström 1987
Christer Malmberg 1987
Lena Mäler 1989
Hans Adolfsson 1989
Helena Looström 1992
Magnus Cernerud 1992
Anna Skrinning 1996
Fredrik Rahm 1998
Mark Sundberg 2000
Stina Lundgren 2002
Foreign students:
Antonio José Reina,
Spain, Ph D student 1991 and 1992
Emmanuel Macedo, France, undergraduate student 1992-93, VSN
1993-94
Isabelle Terrien, France, undergraduate student 1993-94
Christina Arnold, Germany, graduate student 1994
Sylvie Bouchereau, France, undergraduate student 1994
David Berard, France, undergraduate student 1995
Isabelle Bergère, France, undergraduate student 1996
Hélène Strintz, France, undergraduate student
1997
Emmanuelle Petitfils, France, undergraduate student 1997
Achim Böhme,Germany, undergraduate student 1997
Graham Cummings, Great Britain, undergraduate student 1998
Nina Hermanns, Germany, undergraduate student 1998
Elodie Gerard, France, undergraduate student 1998
Laurent Hortala, France, graduate student 1999
Richard Holzwarth, undergraduate student 1999
Sacha Legrand, France, graduate student 1999-
Nils Rackelmann, Germany, undergraduate student 2000
Johann Grognoux, France, undergraduate student 2000
Olivier Schicke, France, undergraduate student 2000
Carole Gayet, France, undergraduate student 2001
Delphine Marches, France, undergraduate student 2001
Sophie Duqeusne, France, undergraduate student 2002
Christian Böing, Germany, undergraduate student 2002