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Details of Grant 

EPSRC Reference: EP/V048961/1
Title: Artificial photosynthesis strategies for synthesis: Combined photoredox and transition metal-catalysed transfer hydrogenation of C-C multiple bonds
Principal Investigator: Cambeiro, Dr XC
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department: Pharm., Chem. & Environmental Sci., FES
Organisation: University of Greenwich
Scheme: Standard Research - NR1
Starts: 14 June 2021 Ends: 31 October 2023 Value (£): 202,477
EPSRC Research Topic Classifications:
Catalysis & Applied Catalysis Chemical Synthetic Methodology
EPSRC Industrial Sector Classifications:
No relevance to Underpinning Sectors
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Panel History:  
Summary on Grant Application Form
The feasibility of chemical reactions is generally governed by the existence of a sufficient thermodynamic driving force pushing them. When performing sequences of reactions to prepare compounds of interest, this driving force is ensured by using in each step highly reactive small molecule reactants with a high energy contents, and the availability and procedence of such reactants determine the limits of how practical and sustainable a chemical process can be. Illustrative examples are oxidations and reductions, two of the main categories in which we classify chemical reactions. In the case of oxidation reactions, molecular oxygen can be used an ideal oxidant, since it is abundant and innocuous and in ideal conditions it can be consumed to produce only water as a by-product. Similarly, we could conceive using water as an ideal reductant, which would result in production of only oxygen as by-product. However, this faces the problem of water not being a good reductant or, in other words, lacking the thermodynamic driving force needed to push the reaction. Instead, the most common reductant used for organic compounds is molecular hydrogen, which is not found in nature and is instead produced in an overwhelming majority from fossil fuels in a process that releases enormous amounts of carbon dioxide.

Remarkably, photosynthetic organisms use water as the reductant in the fixation of carbon dioxide to form carbohydrates and release molecular oxygen, with sunlight providing the required energy. Taking inspiration from this, in this proposal we aim to develop an 'artificial photosynthesis' approach for the reduction of certain types of organic compounds of industrial importance -namely, alkenes and alkynes. To do this, we will need to develop systems where two catalysts operate in a concerted manner, with one using the energy from light to oxidise water (forming oxygen and providing the 'reductive power') and the other reducing the organic compound. Catalysts are already known capable of performing the first of these roles, and in this project we will develop the second, thus bridging the key gap to enable true artificial photosynthesis reactions in organic chemistry.

This investigation will result in more sustainable methods for reduction of alkenes and alkynes which, importantly, are among the largest scale organic reactions performed in chemical industry. Thus, success in this project will contribute towards the development of a more sustainable chemical industry in general, reducing its dependence on the use of fossil sources of carbon. Also, this investigation will produce valuable information on the mechanistic manifolds involved, thus providing facilitating the discovery of other efficient and sustainable reactions in the future.

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