This highly challenging project will explore new synergies in taking electrochemistry towards catalysis and then further to explore electrocatalytic applications.
Flow methodology will be key to the success and with our industrial partners we will make major advancements in the 3.5 years of the project.
The direct use of electrical energy to induce chemical transformations is an efficient and green activation mode of organic molecules. It avoids expensive catalysts and ligands to enable chemical transformations which are otherwise difficult to achieve. Reagent waste is avoided since electrons induce the chemical reactions. Sustainable electricity is becoming increasingly available by exploiting sun and wind energy.
Oxidations typically require stoichiometric amounts of a terminal oxidant and many important transformations in organic synthesis have been developed using this approach. Electrochemical recycling of the oxidant is possible in several cases.
The key requirement for a successful reaction generating and using hypervalent iodine compounds in only catalytic amounts is the ability of the stoichiometric oxidant to selectively make the hypervalent iodine compound in the presence of the substrate. The stoichiometric oxidant has to be carefully selected as it must not react directly with the substrate but allow the re-oxidation of the iodine compound. This can be achieved by pumping only the aqueous iodine(I) solution through an electrochemical microreactor and feeding back the reoxidised iodine(III) species as shown in the bottom part of the catalytic cycle. The current in the electrochemical cell can be adjusted so that only the desired iodine(I) ® iodine(III) oxidation takes place without affecting the substrate.
In the second part of the project, this methodology will be extended to the catalytic generation of chiral iodine(III) reagents for stereoselective reactions. You will build on our experience in hypervalent iodine chemistry as well as flow electrochemistry to address the challenges in this project.
Project aims and methods
You will receive intense training in many areas of synthetic chemistry. The activities described here range from the establishment of analytic techniques to novel organic synthesis. Collaborations with electrochemistry research groups in Germany (Prof. Waldvogel, Mainz), Japan (Prof. Yoshida, Kyoto) and China (Prof. Xu, Xiamen) as well as with Vapourtec (Bury St Edmunds, UK) will enable the student to collaborate with other academic research groups but also appreciate the commercial aspect of microreactor design and development.
This will provide you with a broad training experience in new technology, analytic method development, target synthesis and analytical capabilities.
In addition to the research training and seminar programme, you will receive training in key skills such as data/literature analysis, oral and electronic presentation, scientific communication and problem solving. A weekly group seminar provides an excellent background for developing synthetic capability in organic chemistry including retrosynthesis.
The internal seminars will also allow the development of key presentation skills, to prepare the student for presenting and critically examining scientific publications. Your interaction with others in seminars, workshops and meetings will provide a unique training experience in a multidisciplinary learning environment.
The proposed work on flow electrocatalysis to access compounds with promising features relies on our expertise in synthesis and electrochemistry. The aim is to tackle challenging issues of today and tomorrow through interdisciplinary approaches and research that crosses traditional boundaries. This will broaden and strengthen knowledge transfer activities and result in state-of-the-art training and education for the next generation of researchers.
The proposed project addresses areas of interest to industry and society and will add to the current portfolio of expertise in the School of Chemistry. The research might lead to patentable and commercially promising procedures and products.
Start date: 1st October 2019
Supervisor - Professor Thomas Wirth - https://www.cardiff.ac.uk/people/view/38534-wirth-thomas