A PhD position is available to work with Dr James Taylor at the University of Bath on a project focused on the development of new catalytic processes for the deoxydehydration of diols using modern electrosynthetic technology.
Progress in organic synthesis underpins developments in pharmaceuticals and agrochemicals, chemical biology, and materials science. However, the way in which organic synthesis is performed must undergo significant changes to meet the sustainability challenges of the 21st century, avoiding the use of hazardous materials and the use of wasteful stoichiometric reagents. The development of new catalytic processes is the single most effective way to address these challenges.
The development of efficient processes that reduce oxygen-rich renewable biomass feedstocks into more tractable substrates is an essential component of achieving more sustainable chemical synthesis. The catalytic deoxydehydration of vicinal diols into alkenes is an attractive strategy that removes two oxygen atoms in one-step. To date, scarce and expensive rhenium-based catalysts have been the most widely explored for deoxydehydration in combination with a stoichiometric reductant such as triphenylphosphine. More readily-available vanadium catalysts are also viable for deoxydehydration processes using stoichiometric reductants under harsh reaction conditions, with mechanistic studies suggesting that the V(V) to V(III) reduction step is turnover-limiting.
This project will use state-of-the-art organic electrochemistry equipment to develop new methodology for vanadium-catalysed deoxydehydration reactions under mild electrochemical conditions, avoiding stoichiometric amounts of waste and releasing water as the only by-product. Initial aims will focus on the synthesis and electrochemical characterisation of various vanadium-based catalytic systems. The knowledge gained will then be applied to the optimisation of an electrochemically driven model deoxydehydration reaction using a key proton-coupled electron transfer to provide catalyst turnover and release water as the only by-product. The deoxydehydration process will be optimised in a simple undivided cell at constant potential through variation of the electrode material, electrolyte, buffer, solvent, and temperature using state-of-the-art parallel ElectraSyn® equipment.
Once a suitable procedure has been developed, the scope of the methodology will be assessed through variation of the diol structure, including the use of different substitution patterns and incorporation of various functional groups to test the reaction selectivity. The deoxydehydration protocol can then be applied to polyoxygenated substrates derived from biomass to generate value-added alkenes that may act as more suitable feedstocks for the chemical industry. The established process for electrochemically regenerating the active vanadium species will also provide a strong foundation for further applications to synthetic process that currently require a stoichiometric chemical reductant (or oxidant) to regenerate an active metal catalyst.
This PhD project will provide an opportunity to experience the development of new catalytic methods for applications in organic synthesis, using state-of-the-art electrochemical, reaction screening, and synthetic techniques. We are interested in enthusiastic and motivated researchers and the successful candidate should have a high-class degree in chemistry with some previous experience of practical organic chemistry. Prior experience of synthetic electrochemistry is not required.
For more information, visit: https://jet200.wixsite.com/thetaylorgroup
Applicants should hold, or expect to receive, a First Class or good Upper Second Class Honours degree (or the equivalent) in chemistry with some previous experience of practical synthetic organic chemistry. Prior experience of synthetic electrochemistry is not required. A master’s level qualification would be an advantage.
Enquiries and applications:
Informal enquiries are welcomed and should be directed to Dr James Taylor, [email protected]
Formal applications should be made via the University of Bath’s online application form for a PhD in Chemistry: https://samis.bath.ac.uk/urd/sits.urd/run/siw_ipp_lgn.login?process=siw_ipp_app&code1=RDUCH-FP01&code2=0014
More information about applying for a PhD at Bath may be found here: http://www.bath.ac.uk/guides/how-to-apply-for-doctoral-study/
Anticipated start date: 28 September 2020.