ESR5 Project

Metal-mediated C-F bond activation and C-F bond formation

Recruting institution: CNRS
Diploma-delivering institutions: UPS, UoY
Thesis co-directors: Antoine Simonneau (LCC, Toulouse, FR), John Slattery and Jason Lynam (UoY, York, UK)
Secondment host: Italmatch Chemicals (IT)

Objectives
he selective synthesis of fluorinated organic compounds is crucial for our modern world, as they are ubiquitous in pharmaceuticals, agrochemicals, medical imaging, materials and more. All processes leading to fluorinated chemicals involve the challenges of C–F bond activation, formation and/or functionalisation. This project aims to understand key mechanisms by which transition metal complexes selectively mediate such transformations, experimentally and theoretically, and translate this knowledge into novel, rationally designed catalysts. Complementary early (ETM)[1] and late (LTM)[2] transition metal organometallic approaches will lead to the development of original bimetallic, cooperative fluorination/C–F bond activation catalyses.
Expected Results
(1) Demonstration of fluoride transfer to ETM from at least 5 different fluorinated aromatics leading to CC coupling with a different selectivity to that for LTM, and catalytic implementation of this elementary step. (2) Insight into stoichiometric fluoride and F+ transfer reactions necessary for a catalytic cycle using analogous approaches for a selection of 10 ETM and LTM complexes. (3) Unifying these approaches to add multiple fluorine atoms by sequential electrophilic/nucleophilic fluorinations to provide viable catalytic cycles to a family of highly valuable, partially fluorinated materials in high yield (>90 %) and efficiency (TON > 500).

[1] Q. Dufrois, N. Romero, N. Crespo, A. Pujol, L. Vendier, M. Etienne, in preparation.
[2] L. M. Milner, N. E. Pridmore, A. C. Whitwood, J. M. Lynam, J. M. Slattery, J. Am. Chem. Soc., 2015, 137, 33, 10753–10759; b) L. M. Hall, D. P. Tew, N. E. Pridmore, A. C. Whitwood, J. M. Lynam, J. M. Slattery, Angew. Chem. Int. Ed., 2017, 56, 7551-7556.