thesis
Development of catalysts for asymmetric hydrogenation
- Publication date
- Publisher
Abstract
The application of tetradentate aminoalcohol ligands to the KOtBu-catalysed
hydrogenation of benzophenone has been studied. Hydrogenation was found to
proceed via a transfer hydrogenation process with the ligands acting as hydrogen
donors.
A series of bidentate and tetradentate ligands containing a variety of coordinating
groups including amino, hydroxy, silyl, phosphine and amido functionalities have
been prepared and applied to the transition metal-catalysed asymmetric transfer
hydrogenation of ketones using iron, ruthenium and rhodium metals although none
were found to be enantioselective for the hydrogenation of acetophenone.
A series of asymmetric tethered ruthenium half sandwich complexes have been
applied to the asymmetric pressure hydrogenation of ketones. Studies have
investigated the effect of changing the sulfonamide group, halide and tether length
on the activity of the catalysts. The application of an achiral tethered ruthenium half
sandwich complex as a catalyst for the pressure hydrogenation of aldehydes is also
reported.
A novel synthesis of tethered ruthenium complexes using aryl substitution
methodology has been developed and applied to the preparation of a series of novel
complexes which were found to be highly active for asymmetric pressure
hydrogenation of ketones. The application of the synthesis to the preparation of
poly(methyl methacrylate) supported complexes is also discussed. Application of the
supported catalysts to asymmetric pressure and transfer hydrogenation of
acetophenone has shown potential for the development of an active heterogeneous
catalyst for transfer hydrogenation of ketones in aqueous media