Electrochemical hydrogenations

Lead Research Organisation: University of Bristol
Department Name: Chemistry


Reduction chemistry remains a vital and powerful technique throughout academia and industry in the synthesis of complex organic molecules. Moreover, hydrogenation methods should become more important, as society transitions away from the use of highly reduced petroleum in the chemical industries toward the more oxidised biomass, in which reduction methods are necessary to bring it to application. Despite the importance and prevalence of this reaction to organic synthesis, typical strategies often employ the use of expensive transition metal catalysts, such as iridium or rhodium, in combination with pressurised vessels of explosive hydrogen gas, or, in the case of transfer hydrogenation methods are limited in substrate scope.

As a possible alternative, we aim to explore the use of electrochemistry and base metal catalysis to develop hydrogenation methods that are more environmentally benign, inexpensive and selective.

Planned Impact

The students will be the key beneficiaries of this research as they will be exposed to and be able to exploit a new form of
PhD training in the chemical sciences. In particular they will be able to input to and shape their project before embarking on
it - this will make a key impact on the science compared to the normal PhD route and will produce students who are
motivated and engaged from the start. Aspects of the course such as Brainstorming, regular problem sessions, Outreach
and Public Engagement, and the organization and delivery of the CDT-Syngenta Award to a world-leading academic will
produce students who are more confident in their own abilities. This in turn will have a real impact on their future careers
when making presentations or when interviewed, as well as fast tracking their leadership skills. Other aspects of the
training such as IP, Entrepreneurship and Commercialisation, will help stimulate and prepare these students for developing
their own Start-up ventures based around their science skills. Science and Technology SMEs are increasingly vital to the
UK's economy and if we are to make an impact on the world stage our next generation of scientists must be empowered to
move quickly and flexibly in that direction. At an academic level the science that these students will produce will make an
impact right across the chemical synthesis landscape and will train a new generation of academic unafraid to cross
chemical boundaries. These students promise to contribute to vitally important areas of society such as healthcare,
medicine, energy and food production - all requiring new molecular entities to be produced efficiently and effectively. The
nations health both financially (eg GDP) and physically (eg antibiotics) desperately need innovative new directions. For
example, the Pharmaceutical industry requires a new direction for drug discovery. One ripe area is to explore new 3D
molecular space, a space that just a few years ago would have been avoided due to complexity and expense. If new drug
IP is to be created, and tax revenue thereof, then we must train a new generation of molecule makers who are unafraid to
take on the challenges of this unexplored space and, more importantly, be able to exploit it commercially. We believe that
our Centre will be able to train PhD students with this level of scientific skill and commercial aspiration.
Our industrial stakeholders are invaluable to the the patronage and direction of the Centre and will benefit greatly from
direct interaction with the various cohorts during their tenure in the Centre. For example, by providing the CDT students
with industrial placements, an effective two way knowledge and skills exchange will operate: students will get invaluable
insight into small, medium and large industries; industry will see first hand the highly motivated and skilled students the
Centre produces as well as get access to much of the unique electronic teaching material that the Centre has developed.
Finally the CDT will have a positive impact on supervisor behavior by ensuring collaboration under conditions that are not
forced or artificial. All potential PhD projects submitted for Brainstorming must have at least two supervisors. This can be
either academic -academic (home/away) or academic-industrial. We have found with the current CDT that these proposals
must describe real collaborations or the students are unlikely to select them. This provides the right encouragement for
collaborators to generate strong proposals that will interest all parties, which in turn is leading to high quality publications in
high impact journals.


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Description Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and conformation. The oxidative difluorination of alkenes represents an important strategy for their preparation, yet current methods are limited in their alkenetypes and tolerance of electronrich, readily oxidized functionalities, as well as in their safety and scalability. Utilising electrochemistry, we developed a method whereby new chemical space was accessed by tuning the exact potential applied so that previous untolerable substrates were now conceivable substrate classes. A broad substrate scope was shown to be tolerable as well as several scale-up reactions.
Exploitation Route We hope that through this work, chemists in all professions may be able to access this interesting functional moiety using our method. Not only does our work exhibit the relative ease at which this functional moiety can be incorporated into a drug-like molecule, but also the findings also showcase the overwhelming advantages of using electrochemistry in the way of sustainability, scalability and novel reactivity. We hope that these findings (as well as others in the community) will pursuade those in charge of real-world applications of chemistry to seriously consider the use of synthetic electrochemistry for the sake of a sustainable future.
Sectors Chemicals

URL https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201912119
Description Oxidative fluorination of alkenes 
Organisation GlaxoSmithKline (GSK)
Department Research and Development GSK
Country United Kingdom 
Sector Private 
PI Contribution After conducting research on the project, we have had several meetings with the collaborator (Dr. Darren Poole) to discuss the progress of the project.
Collaborator Contribution Generally, Darren has made some very good suggestions to specific areas of research and at times discussed possible ideas.
Impact No as of yet.
Start Year 2018
Description 19th fluorine postgraduate group meeting, Southampton university 
Form Of Engagement Activity Participation in an open day or visit at my research institution
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact At this conference, I presented a poster to mostly an academic audience, though there were some industrialists present. Generally, this was well received within the community which attended.
Year(s) Of Engagement Activity 2019
Description CDT outreach day 
Form Of Engagement Activity Participation in an open day or visit at my research institution
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Schools
Results and Impact About 60 students attended our teaching laboratories for a school visit, and I personally demonstrated to 6 individuals, teaching them how to extract caffeine from a pot of tea.
Year(s) Of Engagement Activity 2018
Description CDT summer conference 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Industry/Business
Results and Impact The CDT organises an annual conference whereby different cohorts of the CDT present at. In the 2018 conference, I presented the proposal for my project at the time, electrochemical heteroatom functionalisation of alkenes, but last year, 2019, I presented a poster titled "electrochemical difluorination of alkenes". At both of these events I spoke at depth with academics and industrialists, more so at the 2019 conference. I had to the chance to discuss ideas and different avenues my project could possibly take.
Year(s) Of Engagement Activity 2018,2019
Description Enabling technologies workshop, Cardiff university 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Postgraduate students
Results and Impact At this conference, I presented a poster on my difluorination paper, and I discussed the work at length with a number of different academics and students. Overall, the feedback was good.
Year(s) Of Engagement Activity 2019