Reductive cross-coupling/cross-electrophile coupling reactions are powerful synthetic tools which have gained significant attention with the development of Ni-catalysed processes. Many of these happens through single electron transfers (SETs) and radical intermediates, which enable access to different reactivity to those of traditional Pd-catalysed coupling reactions, e.g. coupling with sp3 partners with retention of stereochemistry. Their main drawback, which restricts scaled-up processes, is the need for stoichiometric reductant, e.g. Zn and Mn, and subsequent problems associated with cost and waste.
Electrochemical methods present a possible solution to this problem. The reductant with finely tuned redox potential may be electrochemical recycled in situ, changing its role to a redox mediator. Some early successes with organic reductants have been reported, but mechanistic understanding and development in this area has yet to be taken up by the wider community
In this joint project with AstraZeneca, we aim to develop electrochemical flow processes to enable Ni-catalysed reductive coupling reactions and to generate the required mechanistic understanding for their further development. Flow electrochemical syntheses have the advantages of low over-potential, less side products and higher Faradaic efficiency. The successful flow reactions will be pivotal in the adoption of Ni-catalysed reactions into industrial processes.
The student will receive training on catalysis, electrochemistry, organometallic chemistry, flow chemistry and reaction optimisation. You DO NOT need to have these skills now, only the willingness to learn and develop them. In addition, the student will benefit from working in the highly interdisciplinary research environment and monthly seminar program in the iPRD (https://iprd.leeds.ac.uk). Opportunities to present work and to network will be provided through the iPRD industrial club meetings, AstraZeneca CASE events and other relevant conferences/meetings.
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