Optimisation of catalytic systems using design of experiment methodologies

A Sharpless ligand with a novel triazene core was synthesised in two simple, high yielding steps from cheap, readily available starting materials. The ligand showed good selectivity in the asymmetric dihydroxylation of alkenes, and its optimisation was undertaken in collaboration with Dr D.C. Woods and Professor S.M. Lewis of Southampton University’s Statistical Sciences Research Institute. Using a number of statistical designs and experimental methods, the results showed that the conditions reported and currently used were optimal. In the process of the investigation a greater understanding of the factors affecting the reaction was obtained.

In a second example, C-C bond formation was optimised using a supported palladium catalyst. Four different sulfur containing pincer ligands were synthesized and attached to four different solid supports. Subsequent complexation with palladium gave 16 different polymer supported catalysts which were active catalysts in the Heck reaction. The optimisation of this system with regards to both conversion and palladium leaching was undertaken using the experimental design software, MODDE which showed that solvent had the largest effect on both responses. The cHexyl thiol moiety was superior to its phenyl counterpart which is most commonly adopted. In the Heck reaction of 4-bromo acetophenone the conversion was improved from 30% with large observable leaching to 88% with no observable leaching varying 6 factors corresponding to 5760 possibilities.

University of Southampton

McNamara, Catherine Anne

9d78c411-de46-4f2d-aece-b85732a392c6

2004

McNamara, Catherine Anne

9d78c411-de46-4f2d-aece-b85732a392c6

McNamara, Catherine Anne (2004) Optimisation of catalytic systems using design of experiment methodologies. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)