Senior Lecturer in Organic Chemistry

BSc (St Andrews), PhD (Birmingham).

Tel: 0116 252 2136

email: alison.stuart@le.ac.uk

Research Interests

There is increasing pressure from society on environmental issues and my research is focussed on designing new synthetic methods for developing "clean" organic synthesis. In addition, we are interested in developing novel methods for introducing fluorine selectively into organic compounds.

Fluorous Catalysis

Fluorous chemistry has emerged as a powerful new separation technology for recycling catalysts and reagents that contain long perfluoroalkyl groups. My work has focussed on designing new methods for recycling fluorous catalysts without using the expensive and environmentally-persistent perfluorocarbon solvents. Our group reported the first example of recycling a perfluoroalkylated transition metal catalyst using fluorous solid-phase extraction. Fluorous solid-phase extraction is essentially a filtration that separates the organic products from the fluorous catalysts by flash chromatography on fluorous reverse phase silica gel.

Phase Transfer Catalysis

Phase transfer catalysis is a powerful tool for organic chemists for promoting the reaction between reagents which are mutually immiscible and has been applied to a wide range of organic syntheses in industry. Although phase transfer catalysts normally increase the rates of reaction, increase product selectivity and enable milder reaction conditions to be used, a fundamental problem in their application to industrial processes is the difficulty associated with the recovery and removal of the catalyst from the product. In order to solve this important industrial problem, we are synthesising new phase transfer catalysts derivatised with perfluoroalkyl groups (Fig. 1), which will enable the straightforward recovery and recycling of the catalyst using fluorous solid-phase extraction, and investigating their applications in a range of phase transfer catalytic reactions.

Figure 1. The first crystal structure of a phosphonium salt containing fluorous ponytails.

Organofluorine Chemistry

Within the pharmaceutical and agrochemical industries there is considerable interest in the incorporation of fluorine into biologically active molecules because fluorine can dramatically alter the physical, chemical and biological properties of organic compounds. Consequently, in the fluorine group we are interested in developing new synthetic methods for the construction of C-F bonds and not only do we want to introduce fluorine regioselectively into organic molecules, but we also aim to design new techniques for introducing fluorine stereoselectively for the preparation of chiral organofluorine compounds.

 
Most of these projects involve a multidisciplinary approach where you will gain experience in organic synthesis, fluorine chemistry, ligand synthesis, coordination chemistry, asymmetric catalysis, novel separation technology using fluorous labels and learn how to handle air- and moisture-sensitive compounds. In addition, you will routinely use spectroscopic techniques such as multinuclear NMR (¹H, ¹⁹F, ¹³C, ³¹P), mass spectrometry, infrared, GC and X-ray crystallography.

Selected Publications

• Supported fluorous phase catalysis on PTFE, fluoroalkylated micro- and meso-porous silica.”  E. G. Hope, J. A. Sherrington and A. M. Stuart, Adv. Synth. Catal., 2006, 348, 1635-1639.
• “Insoluble perfluoroalkylated polymers: new solid supports for supported fluorous phase catalysis.”  N. Audic, P. W. Dyer, E. G. Hope, A. M. Stuart and S. Suhard, Adv. Synth. Catal., 2010, 352, 2241-50.
• “A recyclable perfluoroalkylated PCP pincer palladium complex.”  D. Duncan, E. G. Hope, K. Singh and A. M. Stuart, Dalton Trans., 2011, 40, 1998-2005.
• “Syntheses and properties of fluorous quaternary phosphonium salts that bear four ponytails; new candidates for phase transfer catalysts and ionic liquids.”  C. Emnet, K. M. Weber, J. A. Vidal, C. S. Consorti, A. M. Stuart and J. A. Gladysz, Adv. Synth. Catal., 2006, 348, 1625-1634.
• “Perfluoroalkylated 4,13-diaza-18-crown-6 ethers: Synthesis, phase-transfer catalysis and recycling studies.”  A. M. Stuart and J. A. Vidal, J. Org. Chem., 2007, 72, 3735-3740.
• “Di(1H,1H,2H,2H-perfluorooctyl)-dibenzo-18-crown-6: A “light fluorous” recyclable phase transfer catalyst.”  B. Gourdet, K. Singh, A. M. Stuart and J. A. Vidal, J. Fluorine Chem., 2010, 131, 1133-1143.