New Multifunctional Catalysts for Asymmetric Phospho-Transfer

Lead Research Organisation: University of Leeds
Department Name: Sch of Chemistry

Abstract

The development of new catalysts continues to be driven by the need for ever more efficient, cost-effective and selective processes. We are interested in in a particular type of process called phospho-transfer, an extremely broad class of transformation that can be used to make drug molecules, new materials and polymers; indeed, phospho-transfer processes are fundamental to the way our bodies work. This project concerns the development of more efficient and effective catalysts for one powerful example of phospho-transfer, the phospho-aldol (PA) reaction. This process is arguably the most versatile and direct route to phosphorus-containing chemicals such as enzyme inhibitors, antibiotics and antivirals. Within each application, it is the detailed shape of the phosphorus molecule that is crucial in eliciting the required properties.Several teams are developing catalysts which can control the phospho-aldol reaction such that only one shape of product molecule will result. However, significant problems still remain chief amongst which is the fact that no catalyst system been developed which is both highly effective and shape selective but which is capable of working at room temperature in the presence of air and water. Our objectives here build upon our recent discovery of new catalysts which operate at room temperature in the presence of air and water. The key to future exploitation of these new catalysts is to be able to control the shape of the phosphorus products a little better and it is this that we aim to achieve through a combination of computer-aided modelling and synthetic chemistry.

Publications

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Gledhill AC (2010) Asymmetric general base catalysis of the phospho-aldol reaction via dimeric aluminium hydroxides. in Dalton transactions (Cambridge, England : 2003)

 
Description One of the most common and desirable class of catalysts for organic transformations, especially those which are capable of proceeding with control over stereoselectivity, is robustness and activity control.

What we have discovered through this project is that such activity control can be achieved in the phospho-aldol reaction through using a chiral version of a basic silica framework.

Whilst the robustness of the catalyst systems is not yet in the same league as a solid alumina matrix, we have demonstrated the potential for stereoselective phospho-aldol catalysis under mild (ambient & aerobic) conditions, in water.
Exploitation Route I think they key thing would be to improve stereoselectivities and robustness of the catalyst system.
Sectors Chemicals

 
Description Heriot-Watt University 
Organisation Heriot-Watt University
Country United Kingdom 
Sector Academic/University 
Start Year 2006
 
Description Molecularly imprinted polymers for phospho-aldol catalysis 
Organisation University of Leeds
Department School of Chemistry Leeds
Country United Kingdom 
Sector Academic/University 
PI Contribution We have provided the catalytic reaction and expertise associated with the mechanism of this reaction.
Collaborator Contribution Our collaborators have provided the methods and expertise to construct molecularly imprinted polymers and test the resulting abilities to catalyst the phospho-aldol reaction.
Impact None
Start Year 2012