A Sustainable Cooperative Catalysis for the Introduction of SRf groups by C-H functionalization – SCoopCH

Transformations using cooperative catalysis as an efficient tool will be developed in the SCoopCH project for the transition metal catalyzed direct functionalization of C(sp2) and C(sp3) centers with SRf moieties. Hence, during the SCoopCH project, we were able to make significant advances in the highly competitive research fields of homogeneous catalysis and fluorine chemistry. We have been able to develop solutions for more eco-compatible processes allowing novel transformations. We have also been able to study fluorinated motifs of interest (CH2CF3 and SCF2CO2Et). Finally, we were also interested in the introduction of other SR units. We have not only developed a novel palladocatalyzed thiocyanation reaction by C-H bond activation but also applied this concept to access molecular complexity with notably an efficient access to the synthesis of 4-arylisothioazolone derivatives, compounds of interest with high added value.

We have developed new tools for the unprecedented synthesis of SRf-substituted compounds by transition meta catalyzed C-H bond activation. This work has also led us to discover new reactivities and to study new fluorinated groups. All these works have led to publications in peer-reviewed journals, a review and articles in E Eros as well as numerous conferences in (inter)national congresses and seminars where the works have been presented including ISCHA Virtual Symposium, Modern Organic Synthesis Symposium, ESOC 2019, XXIX European Colloquium in Heterocyclic Chemistry, XII International Symposium on Homogeneous Catalysis (2022), 20th European Symposium on Fluorine Chemistry (2022) and the 3rd Eurjoc Virtual Symposium.

The ScoopCH project has allowed us to consolidate our research program in organofluorine chemistry and will serve as a springboard for new perspectives to be developed in the near future, some of which have already been funded (ANR SulCarFluo).

Revues à comité de lecture

1) Q. Zhao, M.-Y. Chen, T. Poisson, X. Pannecoucke, J.-P. Bouillon, T. Besset, Eur. J. Org. Chem. 2018, 6167.

2) M.-Y. Chen, X. Pannecoucke, P. Jubault, T. Besset, J. Org. Chem. 2019, 84, 13194.

3) M.-Y. Chen, X. Pannecoucke, P. Jubault, T. Besset Org. Lett. 2020, 22, 7556.

4) M. Gao, M. Vuagnat, M.-Y. Chen, X. Pannecoucke, P. Jubault, T. Besset* Chem. Eur. J. 2021, 27, 6145.

5) M. Gao, M.-Y. Chen, X. Pannecoucke, P. Jubault, T. Besset Chem. Eur. J. 2020, 26, 15497.

6) L. Ruyet, M. I. Lapuh, V. S. Koshti, T. Földesi, P. Jubault, T. Poisson, Z. Novák, T. Besset, Chem. Commun. 2021, 57, 6241.


Contribution à une encyclopédie (Wiley): Electronic Encyclopedia of reagents for organic synthesis (E eros):
M.-Y. Chen, N-Thiocyanatosuccinimide, 2019, DOI: 10.1002/047084289X.rn02267
M.-Y. Chen, N-thiocyanatophthalimide, 2019, DOI: 10.1002/047084289X.rn02268

The SCoopCH project belongs to the “Major Societal Challenges” defined by the ANR agency. In a society in which the saving energy and the ecological debt are two of the major concerns, it is urgent to mobilize research and innovation forces to develop a “greener chemistry”. The growing awareness of the need to reduce the amount of waste and the number of synthetic steps aroused the interest of the chemist community to elaborate sustainable transformations and new retrosynthetic disconnections based on the principles of “eco-design”. Therefore, as part of the strategies developed by chemists, the direct functionalization of a C-H bond is a promising tool offering unprecedented disconnections, which fulfills the criteria of atom- and step-economy. Besides, due to the impressive ability of the fluorine atom and fluorinated groups to alter the biological and physical properties of molecules, the organofluorine chemistry is a research field of tremendous importance in materials as well as pharmaceutical and agrochemical industries.

The SCoopCH project aims at designing new and sustainable approaches for the transition metal-catalyzed functionalization of aromatic and aliphatic derivatives with various SRf groups (SCF3, SCF2H and SCF2FG) by C-H bond activation. To reach that challenging goal, we intend to bring eco-friendly solutions based on a cooperative catalysis. Proposed methodologies combining original C-H bond functionalization with a focus on cost-efficient first row TMs and new strategies to generate SRf sources, will be disclosed. The ultimate goal of the SCoopCH project is to access new SRf-containing molecules inaccessible so far. These technologies will offer new synthetic routes in agreement with environmental concerns (to minimize the production of waste and atom- and step-economical reactions). In consequence, this project will have a strong impact in pharmaceutical and agrochemical industries, opening new perspectives for the potential industrial applications of C-H bond transformations.