Alison Stuart is a synthetic organic chemist who specialises in the production of fluorine-containing organic molecules and has >60 publications in organofluorine chemistry. She recently developed a new fluorinating reagent, Fluoroiodane, and used it to produce novel fluorinated heterocycles. She is the leader of the Sustainable Synthesis and Catalysis Research group in the School of Chemistry.
My research is focussed on designing new synthetic methodology for introducing fluorine into organic molecules because of the importance of incorporating fluorine into drug candidate molecules. Over the last 60 years fluorinated molecules have proved crucial in the development of new pharmaceuticals and there are approximately 200 pharmaceuticals that contain fluorine. Consequently the chemical industry still needs more efficient, safer and cheaper methods for fluorination.
In 2013 we prepared the fluoroiodane reagent and demonstrated its application as a new fluorinating reagent with 1,3-dicarbonyl substrates. Since then, the reaction scope of fluoroiodane has extended significantly, but most of these reactions required a transition metal catalyst to activate the fluoroiodane reagent. We discovered that fluoroiodane can be activated by hydrogen bonding to hexafluoroisopropanol removing the need for transition metals. A major advantage of using fluoroiodane is that it offers different regioselectivity in fluorocyclisations compared to traditional electrophilic fluorinating reagents (e.g. Selectfluor) and it provides access to novel fluorinated heterocycles.[1,4]
(0) 1. Accessing novel fluorinated heterocycles with the hypervalent fluoroiodane reagent by solution and mechanochemical synthesis, W. Riley, A. Jones, K. Singh, D. L. Browne and A. M. Stuart, Chem. Commun., 2021, 57, 7406-7409.
2. Fluorinations of unsymmetrical diaryliodonium salts containing ortho-sidearms; influence of sidearm on selectivity, A. M. H. Abudken, E. G. Hope, K. Singh and A. M. Stuart, Org. Biomol. Chem., 2020, 18, 6140-6146.
3. Activation of the hypervalent fluoroiodane reagent by hydrogen bonding to hexafluoroisopropanol, H. K. Minhas, W. Riley, A. M. Stuart and M. Urbonaite, Org. Biomol. Chem., 2018, 16, 7170-7173.
4. Intramolecular fluorocyclizations of unsaturated carboxylic acids with a stable hypervalent fluoroiodane reagent, G. C. Geary, E. G. Hope and A. M. Stuart, Angew. Chem. Int. Ed. Engl., 2015, 54, 14911-14914.
5. Single-fluorophore detection in femtolitre droplets generated by flow focusing, R. Weinmeister, E. Freeman, I. C. Eperon, A. M. Stuart and A. J. Hudson, ACS Nano, 2015, 9, 9718-9730.
6. Preparation of iodonium ylides: Probing the fluorination of 1,3-dicarbonyl compounds with a fluoroiodane, G. C. Geary, E. G. Hope, K. Singh and A. M. Stuart, RSC Adv., 2015, 5, 16501-16506.
7. Electrophilic fluorination using a hypervalent iodine reagent derived from fluoride, G. C. Geary, E. G. Hope, K. Singh and A. M. Stuart, Chem. Commun., 2013, 49, 9263-9265.
8. Enantioselective Reformatsky reaction of ethyl iododifluoroacetate with aromatic ketones, M. Fornalczyk, K. Singh and A. M. Stuart, Org. Biomol. Chem., 2012, 10, 3332-3342.
9. Syntheses of α-fluoro-β-hydroxy esters by an enantioselective Reformatsky-type reaction, M. Fornalczyk, K. Singh and A. M. Stuart, Chem. Commun., 2012, 48, 3500-3502.
10. A recyclable perfluoroalkylated PCP pincer palladium complex, D. Duncan, E. G. Hope, K. Singh and A. M. Stuart, Dalton Trans., 2011, 40, 1998-2005.
I am particularly interested in designing new synthetic methodology for the introduction of fluorine into organic molecules. Current research topics are:
1. Difluorination of alkenes
2. Synthesis of novel fluorinated heterocycles
3. Hypervalent iodine(III) chemistry
4. Hypervalent iodine(V) chemistry
I currently lecture in the following core organic courses at the University of Leicester: CH1201 Introductory Organic Chemistry and CH2201 Organic Chemistry. I also lecture at Dalian Institute of Technology: CH3201 Advanced Organic Chemistry.
Press and media
Organofluorine chemistry and hypervalent iodine(III) chemistry
Royal Society University Research Fellow from October 2000 to April 2010
1. “Fluoroiodane: A promising new fluorinating reagent” RSC Organic Division Midlands Meeting, University of Birmingham, 11th April 2016.
2. “Intramolecular fluorocyclisations of alkenes with a stable hypervalent fluoroiodane reagent” 5th International Conference of Hypervalent Iodine Chemistry, Les Diablerets, Switzerland, 3rd-6th July 2016.
3. “Intramolecular fluorocyclisations of alkenes with a stable hypervalent fluoroiodane reagent” Abstracts of Papers 253rd ACS National Meeting & Exposition San Francisco, CA, USA, 2-4th April 2017 FLUO-29.
4. “Designing new strategies for fluorination” Green Chemistry Futures Symposium, Nottingham, 6th February 2018.
5. “Fluorine and Iodine: A powerful combination for fluorination” One Day Symposium on Organofluorine Chemistry: Synthetic Methods and Applications, SCI, Burlington House, London, 9th February 2018.
6. “Synthesis and fluorination of unsymmetrical diaryliodonium salts” 22nd International Symposium on Fluorine Chemistry, Oxford, 22nd - 27th July 2018.
7. “Fluorine and Iodine: A powerful combination for fluorination” Conference on Frontiers in Chemistry, REVA University, Bengaluru, India, 21st - 23rd October 2021.
BSc (St Andrews)
Associate Fellow of the Higher Education Academy