Towards an effective control of the electronic properties in Au(I)-complexes.
From basic principles to asymmetric catalysis.
González Fernández, Elisa
Dissertation
Angenommen am:
2017-02-03
Erschienen:
2017-02-21
Betreuer:
Alcarazo, Manuel Prof. Dr.
Gutachter:
Alcarazo, Manuel Prof. Dr.
Gutachter:
Ackermann, Lutz Prof. Dr.
Gutachter:
Höbartner, Claudia Prof. Dr.
Gutachter:
Meyer, Franc Prof. Dr.
Gutachter:
Stalke, Dietmar Prof. Dr.
Gutachter:
Siewert, Inke Dr.
Zum Verlinken/Zitieren: http://hdl.handle.net/11858/00-1735-0000-002B-7D54-E
Dateien
Name:
with bokkmarksDissertation Elisa González Fernández.pdf
Größe:
21,1 MB
Format:
PDF
Beschreibung:
Dissertation Elisa ...
Lizenzbestimmungen:
Zusammenfassung
Englisch
The dissertation is divided in two different parts, both related with gold(I) chemistry. In the first part, a new class of gold(I)-carbene complexes, the acyclic (amino)-(ylide)carbene (AAYCs) gold(I) chlorides, are presented together with a study of their reactivity. Their cyclic counterparts, (amino)-(ylide)carbenes, have been already reported as ligands to transition metals and present interesting properties, including an excellent σ-donor ability, keeping moderate π-acceptor attributes. Acyclic carbenes have significant stereoelectronic differences compared with cyclic scaffolds, together with the advantage of being easily accessible from the nucleophilic attack to certain metal-isonitrile complexes. Based on the synthesis of acyclic (diamino)carbene-gold(I) chlorides, we have developed a modular strategy for obtaining the AAYC-gold(I) chlorides through the nucleophilic attack of ylides to isonitrile-gold(I) chlorides. Moreover, the presence of additional functional groups on the carbenes side arm allowed their easy derivatisation, leading to the synthesis of heterobinuclear — bearing Rh(I) and Au(I) centres — and cationic AAYC-gold(I) complexes, together with an unprecedented Au(I)→Rh(III) and Au(I)→Ru(II) carbene transmetalation. In the second part of this thesis, TADDOL-based, α-cationic phosphonite ligands are developed and applied to the enantioselective synthesis of hexahelicene derivatives: helical, polyaromatic compounds with potential applications as ligands in asymmetric catalysis,liquid crystals with non-linear optical responses or molecular switches.The use of these novel class of cationic phosphonites as ancillary ligands allowed a highly regio- and enantioselective synthesis of substituted [6]-carbohelicenes through a sequential Au(I)-catalysed intramolecular hydroarylation of achiral diynes. Key for these results are the modular structure of the chiral, cationic phosphonites, and the enhanced reactivity that they impart to Au(I)-centres after coordination due to the presence of a positive charge adjacent to the phosphorus atom.
Keywords: carbenes; gold catalysis; enantioselective catalysis; helicenes; cationic phosphonites
