Photochemical Carbonylation and Hydroformylation (funded by BASF)

Synthesizing amides and esters for the production of agrochemical actives, pharmaceutical actives, and other complicated organic molecules is challenging, as high temperatures need to be applied in current state-of-the-art processes. This often results in limited selectivity and consequently in lower yields and margin of the desired product, in some cases the side products of reactions with limited selectivity will have a negative environmental impact and can even prevent registration of agrochemicals. Novel synthetic approaches are therefore desirable that would yield amides and esters at lower temperatures and with better selectivity. For industrial purposes atom-economic and step-economic processes are desirable, as they can save money and improve sustainability by saving energy for separation, and the disposal of side products through better atom economy and step economy. Moreover, they can make green and bio-derived raw-materials amenable. One particularly attractive way of synthesizing amides and esters is by photochemical carbonylation of aryl-halogenides in the presence of amines or alcohols. This reaction will yield the amide or ester via an intermediate carboxylic acid chloride stage at low temperature and possibly therefore with better selectivity. Moreover, this process is extremely attractive in terms of atom economy and step economy. Photochemistry serves at activating the reatents without the need of putting in heat. The reaction follows a different pathway than the transition metal and opens up a new set of paradigms. Photocatalytic utilization of CO will also be attractive for bulk chemicals produced via classical hydroformylation. Rather than using extremely expensive Rh-based catalysts, in the photochemical pathway H2 and CO to form an aldehyde, a novel, photochemical method will be applied that is based on a different mechanism and therefore has the potential of offering opportunities with regard to selectivity over the state-of-the art. The selection of the metal will affect catalysis and offer an opportunity for tuning the chemical product as well as yield and selectivity. This project will require a vivid interest in organic synthetic chemistry and organocatalysis. It will consider the specifics of photo-redox-chemistry in the framework of an interdisciplinary and holistic cluster of six BASF-funded students on photochemistry.

Academic impact:
Recent advances in data science and digital technology have a disruptive effect on the way synthetic chemistry is practiced. Competence in computing and data analysis has become increasingly important in preparing chemistry students for careers in industry and academic research.

The CDT cohort will receive interdisciplinary training in an excellent research environment, supported by state-of-the-art bespoke facilities, in areas that are currently under-represented in UK Chemistry graduate programmes. The CDT assembles a team of 74 Academics across several disciplines (Chemistry, Chemical Engineering, Bioengineering, Maths and Computing, and pharmaceutical manufacturing sciences), further supported by 16 industrial stakeholders, to deliver the interdisciplinary training necessary to transform synthetic chemistry into a data-centric science, including: the latest developments in lab automation, the use of new reaction platforms, greater incorporation of in-situ analytics to build an understanding of the fundamental reaction pathways, as well as scaling-up for manufacturing.

All of the research data generated by the CDT will be captured (by the use of a common Electronic Lab Notebook) and made openly accessible after an embargo period. Over time, this will provide a valuable resource for the future development of synthetic chemistry.

Industrial and Economic Impact:
Synthetic chemistry is a critical scientific discipline that underpins the UK's manufacturing industry. The Chemicals and Pharmaceutical industries are projected to generate a demand for up to 77,000 graduate recruits between 2015-2025. As the manufacturing industry becomes more digitised (Industry 4.0), training needs to evolve to deliver a new generation of highly-skilled workers to protect the manufacturing sector in the UK. By expanding the traditional skill sets of a synthetic chemist, we will produce highly-qualified personnel who are more resilient to future challenges. This CDT will produce synthetic chemists with skills in automation and data-management skills that are highly prized by employers, which will maintain the UK's world-leading expertise and competitiveness and encourage inward investment.

This CDT will improve the job-readiness of our graduate students, by embedding industrial partners in our training programme, including the delivery of training material, lecture courses, case studies, and offers of industrial placements. Students will be able to exercise their broadened fundamental knowledge to a wide range of applied and industrial problems and enhance their job prospects.

Societal:
The World's population was estimated to be 7.4 billion in August 2016; the UN estimated that it will further increase to 11.2 billion in the year 2100. This population growth will inevitably place pressure on the world's finite natural resources. Novel molecules with improved effectiveness and safety will supersede current pharmaceuticals, agrochemicals, and fine chemicals used in the fabrication of new materials.

Recent news highlights the need for certain materials (such as plastics) to be manufactured and recycled in a sustainable manner, and yet their commercial viability of next-generation manufacturing processes will depend on their cost-effectiveness and the speed which they can be developed. The CDT graduates will act as ambassadors of the chemical science, engaging directly with the Learned Societies, local council, general public (including educational activities), as well as politicians and policymakers, to champion the importance of the chemical science in solving global challenges.