Enantioselective Cobalt-Catalysed Skeletal Rearrangements

Research in the Johnston group broadly focuses on the development of new catalytic reactions for (i) the streamlined synthesis of known small molecules or (ii) unprecedented access to novel building blocks, with potential applications in drug discovery and agrochemistry. To achieve these goals, we utilise and combine various areas of catalysis, including organocatalysis, photoredox catalysis, and base metal catalysis. A key aspect of our approach is ensuring that the reagents, catalysts, and solvents used are sustainable to meet the challenges of modern society. Moreover, to aid the fundamental understanding of these processes and accelerate reaction optimisation, a mechanism-guided approach will be adopted.

Carbocations are common transient species known to participate in a wide range of useful rearrangement and addition reactions but in an unselective manner. In this project, we will employ a cobalt catalyst that, when bound to our starting material, can mimic the reactivity of these reactive intermediates. Unlike free carbocations, the proximity of the modifiable metal catalyst will enable us to control the enantioselectivity of the newly formed bonds. This strategy will harness the under-exploited potential of these reactive intermediates to produce a diverse collection of unique three-dimensional structures, vital to addressing future health and agricultural challenges.

Informal enquiries regarding potential projects and funding options may be addressed to Dr Craig Johnston – email cpj3@st-andrews.ac.uk

Funding Notes

Please see this website for the application procedure, or email chem-pg@st-andrews.ac.uk for more information regarding PhD opportunities at St Andrews. We encourage applications for the NextGenTech Centre for Doctoral Training (View Website) and from Chinese nationals through the St Andrews CSC Scheme (View Website). There are opportunities for self-funded PhD students to make use of the St Andrews Handsel Scheme to fund the difference between home and international fees.

References

For recent examples of our work see: [1] Cobalt-Catalyzed Wagner–Meerwein Rearrangements with Concomitant Nucleophilic Hydrofluorination, Angew. Chem. Int. Ed. 2023, 62, e202308048. https://doi.org/10.1002/anie.202308048. [2] Enantioselective Synthesis of ɑ-Aryl Ketones by a Cobalt-Catalyzed Semipinacol Rearrangement, Angew. Chem. Int. Ed. 2024, e202414342, https://doi.org/10.1002/anie.202414342