- Author
- Title
- Bidentate ligand promoted palladium-catalyzed C–H olefination of aromatic compounds
- Supervisors
- Co-supervisors
- Award date
- 10 October 2019
- Number of pages
- 237
- ISBN
- 9789463804929
- Document type
- PhD thesis
- Faculty
- Faculty of Science (FNWI)
- Institute
- Van 't Hoff Institute for Molecular Sciences (HIMS)
- Abstract
-
Metal-catalyzed C–H functionalization is an attractive strategy to introduce complexity in organic molecules since no pre-functionalization of the starting materials is required. However, the low reactivity of C‒H bonds and the poor selectivity observed in molecules that contain diverse C–H bonds are the main obstacles in the development of efficient C‒H bond transformations. To unlock the full potential of metal-catalyzed C–H functionalization, the discovery of new ligands capable of increasing the reactivity and selectivity of these processes is of central importance. Herein, we described the design, synthesis and evaluation of a new class of bidentate ligands, based on both heteroatom and carboxylic acid functionalities, for C–H functionalization reactions.
In Chapter 2, the development of a new and general methodology for the synthesis of α-substituted phosphinoacetic acids (P,O-ligands) is reported. In Chapters 3–5, the synthesis of new class of ligands in metal catalysis, namely thioethercarboxylic acids (S,O-ligands), is described. The application of these ligands in palladium-catalyzed C–H olefination of simple arenes, including anilines, is presented. The new methodologies proceed efficiently with a broad range of substrates and olefins providing the olefinated product in good yields. We have shown that these methodologies are operationally simple, scalable, and can be used in late-stage functionalization of complex molecules. The S,O-ligand is responsible for the dramatic improvements in substrate scope and the high selectivity observed in these transformations. In Chapter 6, mechanistic studies to understand the role of the S,O-ligand in these reactions are presented. - Persistent Identifier
- https://hdl.handle.net/11245.1/a2da21f4-542a-40b2-91d9-7a3440053c9b
- Downloads
-
Thesis (complete)
Front matter
Chapter 1: C–H functionalization: General introduction
Chapter 2: Synthesis of P,O-ligands and their palladium complexes
Chapter 3: Synthesis of S,O-bidentate ligands and their application in palladiumcatalyzed C–H olefination of non-directed arenes with activated alkenes
Chapter 4: S,O-bidentate ligand promoted palladium-catalyzed C–H olefination of non-directed arenes with allylic substrates
Chapter 5: S,O-bidentate ligand promoted palladium-catalyzed C–H olefination of aniline derivatives
Chapter 6: Mechanistic studies of palladium-catalyzed S,O-ligand promoted C–H olefination of aromatic compounds
Summary; Samenvatting; Acknowledgements; List of publications
Disclaimer/Complaints regulations
If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library, or send a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible.