Dynamic Reaction Monitoring as Enabling Technology for Developing New Selective Catalytic Syntheses in the Fine Chemical Industry

In this project, we will use advanced FlowNMR spectroscopy coupled with other complementary techniques such as UV-vis spectroscopy, mass spectrometry and high-performance liquid chromatography for real-time investigations of molecular solution phase transformations, catalysis with transition metal complexes in particular, with the aim of deriving kinetic and mechanistic information that will allow us to improve existing processes and bring about new reactivity of relevance to industrial fine chemical synthesis.
Example work packages include:
1) Ru- and V-catalysed Meyer-Schuster rearrangement reactions of alkinols. Building on preliminary joint work, establish monitoring of these air-sensitive transformations in flow, utilising selective excitation pulse sequences, hetero-nuclear NMR and two-dimensional techniques to quantify catalyst intermediates. Main focus besides establishing reliable methods for quantitative real-time monitoring of this reaction is understanding and preventing catalyst deactivation to improve productivities.
2) Ru/Rh/Ir-catalysed selective hydrogenation reactions. Extend setup to work under pressures of dihydrogen as reductant, and establish para-hydrogen and deuteration techniques with the aim of increased mechanistic understanding allowing to improve selectivities.
3) Acid-catalysed carbon chain elongation reactions. Develop advanced 13C FlowNMR methods and reaction engineering solutions including mass spectrometry sampling to allow tracking C3 and C4 extension reactions at high temperature and pressure with the aim of understanding the reaction pathway.
4) Cu-catalysed aerobic oxidations of phenols to quinones. Explore the possibility of utilizing paramagnetic NMR spectroscopy in flow with the aim of establishing a method for investigating oxidation reactions proceeding through open-shell species.
The work will be carried out in Bath's Dynamic Reaction Monitoring Facility, supervised by Dr Ulrich Hintermair. DSM offer strategic advice and project support in form of access to R&D materials and foreground IP as well as placement opportunities. Project updates by email or telephone were agreed to occur every 3 months, project meetings in person or via Skype every 6 months, and written reports every 12 months.