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Gaining Selectivity Control in Homogeneous Catalytic Ester Formation and Reduction with Multi-Nuclear High Resolution FlowNMR Spectroscopy


Project Description

Lead supervisor: Dr Ulrich Hintermair (https://www.hintermair-research.com/)
University co-supervisors: Dr John Lowe & Dr Catherine Lyall (http://www.bath.ac.uk/research-facilities/dynamic-reaction-monitoring-facility/)
Industrial co-supervisor: Dr Antonio Zanotti-Gerosa (Johnson Matthey Catalysis & Chiral Technologies)

The project:

The catalytic reduction of esters to alcohols is an exciting recent development of homogeneous catalysis with a clear potential for significant industrial impact. If only a fraction of the current industrial reduction reactions using stoichiometric hydride reagents (e.g. NaBH4, LiAlH4, DIBAL, etc.) could be replaced with highly active and selective catalysts utilising H2, the environmental benefits would be enormous. Hydride reductions have complex and often hazardous work-up procedures that generate large amounts of waste, while homogeneous catalytic reductions are operationally simple, clean reactions with 100% atom economy that require little to no work-up.

However, the potential of ester reduction catalysts can only be exploited if they can be shown to be a reliably superior choice to established technologies, and some important hurdles remain before the technology can be operated at full potential in an industrial environment. In particular, most homogeneous ester hydrogenation catalysts operate with a bifunctional mechanism under strongly basic conditions, which limits applications on chiral substrates (which often are prone to racemization) and substrates with even mildly acidic functional groups (e.g. phenols, malonates….). Currently there exists limited understanding of the mechanism and how reaction conditions (e.g. pH, water, solvent, base, deactivation/inhibition) affect the catalytic cycle and product distribution obtained. Empirical optimisation approaches are being pursued to improve the technology, but a rational, mechanism-guided investigation offers the opportunity to solve these key challenges. An understanding of the reaction pathway also promises to bring about new reactivity and allow capturing key intermediates to achieve new transformations. For instance, ester reduction to aldehyde, amide reduction to amine, and the reverse reactions of coupling alcohols/amines to esters/amides all represent highly sought-after transformations that are difficult to achieve selectively with existing catalysts due to a lack of mechanistic understanding. Understanding the generation and structure of the key hydride intermediates might allow devising new catalysts that operate under milder hydrogen transfer conditions rather than with elevated H2 pressure and strong bases.

Bath’s Dynamic Reaction Monitoring (DReaM) Facility offers a unique combination of complementary operando techniques currently comprising multi-nuclear FlowNMR, head-space MS, liquid phase MS, UV-vis, and HPLC. All of these are part of a fully integrated and computer-controlled reaction monitoring system that is able to track reaction intermediates and products in real time to give comprehensive insight into complex reaction networks (such as ester reduction catalysis). Selective excitation pulse sequences can detect sub-micromolar traces of metal hydride intermediates, and we have recently implemented fast & quantitative {1H}31P acquisition parameters to track ligands bound to the metal during catalysis. Advanced reaction progress kinetic analyses using variable time normalization analysis (VTNA) will be used to quantify deactivation phenomena to derive methods for minimizing/shunting inhibition pathways.

Johnson Matthey is a global specialty chemicals company and international leader in sustainable technologies and catalysis who will provide project support. The JM research centre in Cambridge (UK) is a state-of-the-art facility with more than thirty researchers and support personnel dedicated to the development of new catalytic solutions for the pharmaceutical, flavour and fragrances and agrochemical markets.

Candidate:

Applicants should hold, or expect to receive, a First Class or high Upper Second Class UK Honours degree (or the equivalent qualification gained outside the UK) in a relevant subject. A master’s level qualification would also be advantageous.

Essential skills/interests are organometallic chemistry, homogeneous catalysis, NMR spectroscopy, kinetics, mechanisms.

Applications:

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=0013

Please ensure that you quote the supervisor’s name and project title in the ‘Your research interests’ section.

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: 30 September 2019.

NOTE: Applications may close earlier than the advertised deadline if a suitable candidate is found; therefore, early application is strongly recommended.

Funding Notes

Candidates applying for this project will compete for a studentship covering Home/EU tuition fees, a training support fee of £1,000 per annum and a tax-free maintenance allowance at the RCUK Doctoral Stipend rate (£14,777 in 2018-19) for a period of 3.5 years.

Due to the nature of the funding source, only UK and EU applicants are eligible for this studentship; unfortunately, applicants who are classed as Overseas for fee paying purposes are NOT eligible for funding.

References

Ester hydrogenation:
Pidko et al., Chem. Soc. Rev. 2016, 44, 3808.
Gusev et al., Angew. Chem. 2017, 56, 6228.
Mechanisms in homogeneous catalysis:
ACS Catalysis 2014, 4, (3), 973.
Organometallics 2017, 36 (18), 3578.
Reaction monitoring by FlowNMR:
Catalysis Science & Technology 2016, 6, (24), 8406.
Chem. Comm. 2018, 54 (1), 30.

How good is research at University of Bath in Chemistry?

FTE Category A staff submitted: 33.10

Research output data provided by the Research Excellence Framework (REF)

Click here to see the results for all UK universities

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