Exploiting the Non-innocent Ligand Reactivity of Metal Bis-dithiolenes: Towards the Catalytic Synthesis of Chiral Thioether Ligands and other Synthetic Targets

• Main Author: Moscattini, Joshua
• Other Authors: Fekl, Ulrich
• Language: en_ca
• Published: 2012
• Subjects: Dithiolenes; Chiral Ligand; Ligand Non Innocence; Asymmetric Catalysis; Platinum; Palladium; Hetero-Diels-Alder; 0488
• Online Access: http://hdl.handle.net/1807/33457

Asymmetric catalysis is one of the most effective ways to control a target molecule’s stereochemistry. Through the development of a wide variety of chiral transition metal complexes, synthetic chemists are given the tools they need to synthesize the desired enantiomer of numerous compounds. This work focuses on exploiting the non-innocent ligand reactivity of metal bis-dithiolenes with multiple conjugated π systems in order to synthesize chiral ligands. Recent work has shown that platinum bis-dithiolene reacts with dienes stereoselectively to form a racemic mix of C2 -chiral thioether ligands. The present contribution will show approaches to synthesizing chiral dienes and organometallic complexes with potential applications for asymmetric allylic substitution reactions. Dienes with various chiral auxiliaries were reacted with platinum dithiolene and monitored through NMR spectroscopy. Attempts to synthesis palladium bis-dithiolene complexes, not previously seen in the literature were made, and the reaction of α-β unsaturated ketones with metal bis-dithiolenes was explored.