New Catalytic C-H Activation and Decarboxylation Chemistry for Synthesis

Lead Research Organisation: University of Manchester
Department Name: Chemistry

Abstract

The proposed research looks to create new ways of making molecules using catalysts - catalytic chemistry. A catalyst is something added in very small amounts to a reaction that will make it faster, and they play a very important in modern chemistry. Up to 90% of chemically produced materials have used a catalyst in their production - the enzymes in washing powder are a type of biological catalyst that helps break down organic stains on clothes, for example. The catalytic converter in a car contains precious metal catalysts that help convert harmful nitrogen monoxide fumes into harmless nitrogen gas.

Catalysts can dramatically accelerate chemical reactions, to the extent where some impossibly slow processes become highly efficient when performed under catalytic conditions. The challenge is matching up the right catalyst with the right chemical reaction. This research proposal will look at ways of manipulating the carbon-hydrogen bond through catalysis. The C-H bond is often thought of as inert, being the most common bond in organic chemistry and frequently a by-stander in chemical reactions. Its common occurrence, though, gives it tremendous potential as a site for chemical manipulation - if ways can be found to do this selectively under mild reaction conditions. We now have methods in place to achieve C-H activation using transition metal catalysis, and we are looking to exploit their economic and environmental benefits in streamlined chemical synthesis.

We will apply the catalytic reactions we discover to make a class of molecule called heterocycles. Heterocyclic compounds have enormous importance in our society: DNA, sugars, proteins, the molecules of nature, drugs, insecticides and vitamins represent just some of the classes of heterocycle essential to the way we live our lives. As a result, the discovery of new and improved ways to synthesise new and improved heterocycles is at the forefront of modern chemistry research. The use of C-H activation offers substantial improvements to both the synthesis of existing heterocyclic compounds and the discovery of new ones, which can have wide application in medicine, engineering and agriculture.

Planned Impact

Catalysis plays a central role in the discovery of new chemical reactions and processes. Catalytic C-H activation presents a new way of thinking about how molecules can be made, offering quicker and more efficient routes to the molecules that are central to society's medicine, food, materials and energy requirements. The impact of the proposed research is thus very broad, as it changes the way molecules will be made and, by extension, how they will be used.

Who will benefit and How?

Academic researchers from other disciplines: Our C-H activation chemistry will simplify and extend synthetic chemistry for cross-disciplinary applications. The power of C-H activation offers a step change in efficiency and can significantly accelerate the business of synthesis. The design of high-reactivity catalysts for C-H bond activation enables simple, labour-saving chemistry that can produce high value molecules with a minimum of operational difficulty.

Teachers and trainers of young scientists. By introducing a new way of looking at the C-H bond, which is generally considered an inert bystander in early to mid-stage chemistry teaching, we introduce a new dimension that can capture the imaginations of students looking to understand chemistry and see its impact in society.

Industry: The proposed catalytic chemistry will expand the scope, expediency and diversity of molecular synthesis for use in all sectors of the fine chemicals industry. Fine chemical research underpins chemical sales of over 500 billion euros each year in the EU and is central to the economic performance of nearly all member states. Catalytic C-H activation is a break-through concept in how molecules are made and will directly impact the economic performance of companies and, in turn, the UK economy. Examples of industrial scientists who will be influenced by our proposed research are process chemists in agro- and medicinal chemistry, looking to streamline synthesis and reduce waste and costs; and discovery chemists looking for new molecules or materials.

Environmental and Energy scientists and policy makers: Catalytic C-H activation will be integral to future sustainable manufacturing through the selective functionalisation of biomass to obtain feedstocks. The proposed decarboxylation research will impact thinking on how to process intractable ligno-cellulose biomass that features multiple carboxylic acid functionality. Methane oxidation to methanol and carbon dioxide capture through C-H activation are major areas of energy research that likewise are aligned to the research goals we are pursuing - how to activate a C-H bond with a metal catalyst under mild conditions, and exploit it to make useful molecules for society.

Society : The sphere of impact of synthesis is vast in terms of the man and woman on the street using, wearing and consuming materials that have come into being through chemistry invention.The end-products of fine chemical synthesis include new medicines and medical procedures (imaging), agrochemicals and food technology, flavours and fragrances, and organic materials which represent the next generation of electronic devices and displays. Bulk chemical synthesis produces fuels, paints, coatings, adhesives and polymers as building blocks for devices and manufacturing - C-H activation can play a role in the invention and production of all these molecules - by innovating at the level of reaction discovery in our laboratory we can produce molecules that impact the way people live their lives.

Publications

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Description The research has uncovered a number of methods of making molecules in a more streamlined and efficient way. These considerations are fundamental to sustainable chemistry - how can we produce the molecules that structure our society using less energy, creating less waste, and for less cost? We have demonstrated innovation in two areas in this research - introducing fluorine into molecules in a new way, and making carbon-carbon bonds in an efficient way using copper catalysis.
Exploitation Route Novel catalysis is essential to chemical invention and manufacture. We have shown that copper catalysis can be used to effectively make two carbon-carbon bonds in a single operation, to access drug-like molecules for biological testing. These findings will be exploited by the fine chemicals industry as scientists look for ways of quicker and more efficient synthesis of drugs, agrochemicals, materials and other key components of the chemical base of the UK.
Sectors Agriculture, Food and Drink,Chemicals,Pharmaceuticals and Medical Biotechnology