Scientific work and main results achieved so far:
1 We initially started the project by trying to develop reactions of nitrogen radical with very electron rich olefins like vinyl and allyl trifluoroborates – an important class of building blocks used for examples in the Nobel Prize winning Suzuki cross-coupling reaction.
This project was based on the idea that as nitrogen radicals are very electrophilic species, they should undergo very facile reaction with electron rich pi-systems. After a detailed reaction optimisation we were able to develop such a process and therefore provide a platform for the assembly of allyl and vinyl-substituted amides. However, the yield for this transformation were very low so we realised that even more electrophilic radicals were required to harness the full potential od this reactivity. We therefore screened highly electrophilic malonyl-type radicals. These species were efficiently generated by photoredox catalysis using the organic dye eosin Y and underwent a very efficient and selective reaction with the trifluoro-borates building blocks. This reactivity has provided a photo-organocatalytic Suzuki-type cross-coupling reaction and we applied it to the modification of veterinary products and sunscreen products.
Publication: ACS Catal. 2017, 7, 4126 and Org. Biomol. Chem. 2019, 17, 1839.
2 We tackled the fundamental question of introducting an amino-functionality onto an aromatic ring in place of a C–H bond. This is a fundamental challenge in synthetic chemistry as all methodologies able to aminate aromatics require functionalised arenes like aryl halides or aryl-boronic acids. We have tackled this project in two steps. Initially we have studies the reactivity of hihgly electron rich hydroxylamine derivatives (prepared in four steps) as nitrogen-radical precursors and we demonstrated that these species can react with several un-functionalised aromatics.
Publications: Angew. Chem. Int. Ed. 2017, 56, 14948.
3 We decided to tackle the ultimate challenge of forming C–N bonds between an aromatic and an amine without any functionalisation at both sides. This was possible by generating in situ N-chloroamines, which proved very powerful intermediates for achieving this goal. This work has received signficant publicity, including a press release from AstraZeneca (
https://www.astrazeneca.com/content/astraz/media-centre/articles/2019/lighting-the-path-to-simplified-chemical-reactions16042019.html(odnośnik otworzy się w nowym oknie)).
Publications: Nat. Chem. 2019, 11, 426.
Career development work and main results achieved so far:
1 The awardee has been involved in the superivison of several PhD and MChem students in the Host group. The ability to effectively supervise, coordinate and support young scientists is a fundamental skill required both in academia and industry. The awardee has excelled here and was able to efficiently manage and assist the students and also provide constructive feedbacks during formal weekly meetings with the Host supervisor.
2 IThe awardee has run 1st, 2nd and 3rd year tutorial at the University of Manchester. This activity involved marking MChem students assignements and then running a 1h tutorial to revise general concepts and promote scientific discussion. Before starting this activity, the awardee attended several training workshops offered by the University on the most effective approaches to facilitate students learning.
3 In the final months of the Fellowship, the Awardee has helped the Host group to run an outreach acitity at the Manchester Grammar School where he thought photochemistry to a class of 16 pupils.
4 Towards the end of the Fellowship the awardee has been able to propose a novel research project and he completely developed and executed it with the help of one visiting PhD student and one MChem student. This proejct was succesfully published in the RSC journal Organic and Biomolecular Chemistry and the awardee was the corresponding author.
Impact related work and main results achieved so far:
Academic impact. The results of this Fellowship have been pubblished in high-impact chemistry journals that have increased the visibility of both the awardee and the Host supervisor. As an example, a group of PhD students in the US have created a YouTube channel called the CycloEdition and created a video to discuss and explain the relevance of the chemistry developed by the awardee during the Fellowship (
https://www.youtube.com/watch?v=ujjt-PlrUvg&app=desktop(odnośnik otworzy się w nowym oknie)).
Industrial impact. Some of the results of this project have been developed in collaboration with AstraZeneca. Our work has provided an effective and industrially feasible way of forming carbon-nitrogen bonds. The host group is currently developing other projects in collaboration with AstraZeneca.
Societal impact. The Host supervisor has initiated an outreach activity at the Manchester Grammar School in Manchester where 16 students are run a photochemical experiments every Wednesday. This activity has provided the students exposure to chemistry research. This project has sparked significant interest into these pupils about science and more specifically the use of light in chemistry.
