The development of new procedures for the production of biologically and industrially relevant compounds still remains a big challenge in chemistry. The biaryl motif is ubiquitous among a wide range of compounds of industrial importance. For example, the biaryl skeleton is found in molecular switches and motors, agrochemicals or medicines such as antifungal, anticancer, antibiotics, anti-inflammatory treatments. These properties make the biaryl functionality a highly desirable synthetic target, for both commercial and research purposes. In this context, C-H arylation has been acknowledged as a useful alternative to traditional cross-couplings, replacing the organometallic coupling partner by a non-prefunctionalised substrate in the reaction with a haloarene. Approaches for the development of Ru-catalysed C-H arylation methodologies are presented herein. The introduction provides a general overview about different strategies employed in metalcatalysed direct C-H arylation methods. The rational behind selectivity and reactivity are also thoroughly discussed. The second chapter describes studies on the C-H activation of perfluorinated arenes by Ru(II)-species. The synthesis of unprecedented aryl rutyhenium complexes and mechanistic considerations on the metalation of the arene are presented. In the last part of the second chapter the development of a bis-cationic rutehium(II) complex able to catalyse direct C-H arylation of electron-poor arenes with bromoarenes in the absence of any directing group is described. A complete mechanistic analysis, along with the scope of the methodology, is therefore given.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:765820 |
| Date | January 2016 |
| Creators | Simoneti, Marco |
| Publisher | Queen Mary, University of London |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://qmro.qmul.ac.uk/xmlui/handle/123456789/24249 |
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