Organic Dications: Synthesis, Reactivity and Applications

One of the principal factors governing the reactivity of substances is their degree of electric charge - in simple terms, opposite charges attract, so the more charged a compound is, the more reactive it should be. Until now, the way to produce compounds that are highly electrophilic (very positively charged) was to use ''super-acids'', i.e. acids that are stronger than 100% sulfuric acid. Performing chemistry in super-acid has been very useful for understanding the reactions of super-electrophiles derived from hydrocarbons. This proposal addresses the preparation of novel and highly electrophilic species in molecules containing heteratoms (usually nitrogen) in organic solvents, and looks to study their reactivity. It has potential applications across a broad range of chemical reactions, and it could also have relevance to UK plc through taking first steps in the development of catalysts for performing reactions (like Friedel-Crafts reactions) that have traditionally used environmentally harmful reagents such as aluminium trichloride. Super-electrophile chemistry may also explain some of the biggest puzzles in bioorganic reaction mechanisms, involving reactions that are required for DNA synthesis (the formation of thymine derivatives from their uracil counterparts) and protein synthesis (preparation of methionine from homocysteine - methionine is the starting amino acid for all genes during translation). Even the mysterious but potentially very useful production of methane from carbon dioxide that is achieved by bacteria, could depend on the chemistry of the superelectrophiles that are discussed in this proposal.This is a new adventure in chemistry that we expect to have widespread applications.

1. Who will benefit from this research? 2. How will they benefit from this research? (i) Chemists in academic and industry laboratories will benefit.... through discoveries of new chemical reactions. For example, we may find a way to avoid the use of aluminium chloride in Friedel-Crafts reactions, thereby avoiding waste and pollution. Furthermore, our reactions will provide energy savings by taking place at ambient temperature [due to the high reactivity of our intermediates]. (ii) The PDRA and PhD student engaged on this research programme will benefit through being trained in a cutting edge area of chemistry and through publications in high-impact journals. (iii) Society in general will benefit.....through a greater understanding of how methanogenic bacteria use carbon dioxide as a chemical feedstock. This could lead to new catalysts that use excess carbon dioxide for useful tasks. (iv) Biochemists will benefit through a better understanding of how methyl transfer occurs in nature. 3. What will be done to ensure that they have the opportunity to benefit from this research? Where appropriate, the discoveries will be protected by patent in first instance, through the Research and Innovation Department at the University of Strathclyde, with a view to licensing as soon as possible, so that the discoveries may be deployed for general benefit of society. The research will be published as soon as possible, in journals of the highest calibre, to maximise the audience. The work will be publicised at international and national Conferences and through popular media, where apropriate. The PDRA and PhD student will be exposed to a modern comprehensive training in a 21st century research school (WestCHEM), involving them in weekly group meetings, and in the preparation and presentation of lectures, posters and publications on their research.