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Details of Grant 

EPSRC Reference: EP/M026221/1
Title: Catalytic generation and harnessing of reactive intermediates
Principal Investigator: Jones, Dr C R
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department: Sch of Biological and Chemical Sciences
Organisation: Queen Mary University of London
Scheme: EPSRC Fellowship
Starts: 01 October 2015 Ends: 30 September 2020 Value (£): 675,133
EPSRC Research Topic Classifications:
Catalysis & Applied Catalysis
EPSRC Industrial Sector Classifications:
No relevance to Underpinning Sectors
Related Grants:
Panel History:
Panel DatePanel NameOutcome
12 Feb 2015 EPSRC Physical Sciences Chemistry - February 2015 Announced
10 Mar 2015 EPSRC Physical Sciences Fellowships 10, 11, 12th March 15 Announced
Summary on Grant Application Form
Reactive chemical intermediates are short-lived and high-energy molecules. Whilst it is inherently demanding to exploit the high levels of reactivity of these species, the potential benefits are compelling. Great opportunities are afforded to conduct powerful new chemical and biological processes, with applications in medicine and materials development amongst others. The goal of this proposal is to provide new methods to harness reactive intermediates and hence facilitate reactions of immense utility.

We will focus on intermediates called arynes; molecules in which one of the three carbon-carbon (C-C) double bonds in a benzene ring has been replaced with a C-C triple bond. Incorporating this triple bond causes the ring to become highly strained and thus highly reactive. Arynes are extremely useful as they enable rapid generation of complex benzene ring-containing products that are common in pharmaceuticals, agrochemicals, materials and dyes.

Despite recent advances, methods for an ideal scenario whereby arynes are prepared using a catalyst - a small amount of a substance that promotes a reaction but is not consumed and can thus be recycled - are extremely rare and no general procedure exists. As a result, our long term goal will be to develop a general strategy for catalytic aryne synthesis that also exploits abundant chemicals. There are myriad potential benefits, from the development of new chemical reactions for application in healthcare and manufacturing, to the environmental issues of reduced waste production and the use of more plentiful starting materials.

One example of a cheap bulk chemical for this process is phenol (a benzene ring with an oxygen atom attached), with 60,000 commercially available analogues also offering great potential for structural diversification. By attaching an activating group to the oxygen, we will investigate strategies that enable the proximal addition of a catalyst onto the benzene ring. This catalyst can then interact with the adjacent activating group to aid elimination of the two species from the ring, producing an aryne. The catalyst will then be free to add to another activated phenol ring and thus the cycle is established.

We will also look to subsequently exploit the reactivity of arynes in demanding reactions, such as manipulating the ubiquitous carbon-hydrogen (C-H) bond. Breaking a particular C-H bond and replacing that hydrogen with another atom is extremely desirable, as it means valuable compounds can be made directly from cheap hydrocarbon materials. However, this process is very difficult due to the strength of the C-H bond and most progress has been made using metal catalysts that can be expensive and toxic. Here we will utilise the high reactivity of arynes to develop new complementary metal-free methods for selective C-H bond breaking, involving an initial hydrogen ion transfer from the hydrocarbon compound onto the aryne. This novel process results in two oppositely charged molecules, and we propose that via the recombination of these charges, a new C-C bond will be made. Studies into hydrogen ion transfer onto an aryne will commence with systems where the two components are in the same molecule, tied together in close proximity to aid the reaction. As our understanding increases, we will see whether they can be part of different molecules, which is anticipated to be more challenging. Crucially, we have a preliminary result to support this unique concept.

This research area has been chosen because arynes enable rapid construction of useful complex molecules. Developing these new methods will enable chemists to make drug, polymer, dye and agrochemical compounds more efficiently, and maybe even prepare molecules that are currently inaccessible. These advances can benefit wider society through the development of drugs to treat illnesses, herbicides and pesticides to improve global food production and by harnessing more sustainable chemical feedstocks.

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