About the Project
The Green Chemistry Centre of Excellence (GCCE) has longstanding experience in the synthesis and development of novel, bio-derived solvents, and has recently developed several new exciting candidates to replace traditional solvents such as hexane, toluene, NMP and DMF.
Increasing legislative strain is being placed on traditional solvents and therefore safer alternatives which have been proven in applications are urgently needed. As such, this PhD will principally focus on application testing of novel bio-based solvents developed within the GCCE and is expected to include, but not be limited to, solvent effects on reaction chemistry, applications in purification and analysis, and enzyme catalysed reactions. Initial areas of focus will concern the testing of solvents in applications where ethers, toluene or chlorinated solvents are normally used, especially in synthetic organic chemistry. One such example would be the use of our recently developed 2,2,5,5-tetramethyloxolane (TMO) as a solvent for α-lithation and subsequent electrophile trapping of N-Boc heterocycles (e.g. piperidine and pyrrolidine). Traditional solvent systems for this reaction include 1) tetrahydrofuran (THF) and 2) diethyl ether with the addition of TMEDA. THF negates the need for addition of TMEDA but its use leads to undesirable side reactions due to the presence of its own acidic α-protons.6 TMO contains no such acidic α-protons and could therefore prove an excellent alternative for this application (Scheme 1), a reaction widely used in the synthesis of important active pharmaceutical ingredients (e.g. the synthesis of the blockbuster hepatitis C drug Telaprevir).7 Other organometallic reactions of interest for exploring TMO and cyrene as solvents include lithium-halogen exchange and magnesium-halgoen exchange.
The research will also be assisted by in silico calculations, directing solvent choices to maximise the efficiency of the applications. Calculated properties and experimental data gathered for the various reactions will be used in an iterative approach to optimise the computational models used.
This work is co-sponsored by Sigma-Merck. The PhD student will engage with representatives of the company to take the selected bio-derived solvents from research to market. It is anticipated the student will spend up to 3 months of their time at the partner institution over the length of the PhD. Demonstration of these solvent in new applications will lead to maximising their potential positive impact, market share and volume of production
The PhD project will be fully funded under the “RenewChem” initiative (https:// york.ac.uk/chemistry/research/green/renewchem/). RenewChem students are expected to take a wider interest in green and sustainable chemistry than a conventional Ph.D. This includes a specially designed training module that introduces topics including Change Management, Environmental Impact and the Commercialisation of Science. In addition to collaborating with a company, RenewChem students have the opportunity to spend a period of their research in a laboratory at one of our collaborating green and sustainable chemistry centres (g2c2.greenchemistrynetwork.org).
All research students follow our innovative Doctoral Training in Chemistry (iDTC): cohort-based training to support the development of scientific, transferable and employability skills. All research students take the core training package which provides both a grounding in the skills required for their research, and transferable skills to enhance employability opportunities following graduation. Core training is progressive and takes place at appropriate points throughout a student’s higher degree programme, with the majority of training taking place in Year 1. In conjunction with the Core training, students, in consultation with their supervisor(s), select training related to the area of their research.
Project specific training will include advanced organic synthesis methods for an array of standard chemical transformations, including large scale reactions to synthesise solvents in bulk (> 1 kg) and the use of computational modelling to help guide the research towards suitable target applications. Clean synthetic methods will be used throughout the project and may include training in the use of microwave, heterogeneous catalysis and flow reactors. Training will also be offered by Sigma-Merck in pilot scale synthesis of promising solvents and in broader application testing outside of the Universities expertise.
The Department of Chemistry holds an Athena SWAN Gold Award and is committed to supporting equality and diversity for all staff and students.
• Candidates should submit an online application for a PhD in Chemistry by 6 April 2018
• Supervisors may contact their preferred candidates either by email, telephone, web-chat or in person
• Supervisors will select their preferred candidate from those that meet the University’s entry requirements
• Candidates will be notified of the outcome by email
The PhD is available to start between 1 May 2018 and 1 October 2018 depending on the availability of the successful candidate.
References
1) F. Byrne, B. Forier, G. Bossaert, C. Hoebers, T. J. Farmer, J. H. Clark and A. J. Hunt, Green Chem., 2017, 19, 3671.
2) J. Sherwood, M. De bruyn, A. Constantinou, L. Moity, C. R. McElroy, T. J. Farmer, T. Duncan, W. Raverty, A. J. Hunt and J. H. Clark, Chem. Commun., 2014, 50, 9650.
3) A. Iemhoff, J. Sherwood, C. R. McElroy and A. J. Hunt, Green Chem., 2018, 20, 136.
4) S. B. Lawrenson, R. Arav and M. North, Green Chem., 2017, 19, 1685.
5) J. Sherwood, H. L. Parker, K. Moonen, T. J. Farmer and A, J. Hunt, Green Chem., 2016, 18, 3990.
6) V. Antonucci, J. Coleman, J.B. Ferry, N. Johnson, M. Mathe, J.P. Scott and J. Xu, Org. Process Res. Dev. 2011, 15, 939.
7) G.J. Tanoury, M. Chen, Y. Dong, R. Forslund, V. Jurkauskis, A. Jones and D. Belmont, Org. Process Res. Dev. 2014, 18, 1234.