ESR1 Project

Olefin metathesis catalysts with high Z-selectivity

Recruting institution: CNRS
Diploma-delivering institutions: UPS, UW
Secondment host: Fundacion Tecnalia Research & Innovation (ES)


Objectives
The olefin metathesis reaction being under thermodynamic control, E-olefins are generally obtained preferentially. Significantly, the development of an efficient and general Z-selective metathesis catalyst still remains a great challenge.[1] Merging the complementary expertise of the two teams,[2,3] this project aims at developing highly modular, efficient and general Z-selective Ru-based metathesis catalysts, which will include specifically-designed five- and six-membered cyclometallated NHC ligands associated with monoanionic bidentate ligands.
Expected Results
At least one class of efficient and robust pre-catalysts (<0.1 mol%) for highly stereoselective (Z:E ratio > 95/5) C=C bond formation in olefin Ring Closing Metathesis (RCM) and Cross Metathesis (CM) reactions, and with general applicability to functionalized substrates incorporating ester, alcohol, ether, amide groups… Technology transfer to industrial level planned through secondment in Tecnalia. The ESR will also acquire a strong background in synthetic chemistry and homogeneous catalysis.

[1] O. M. Ogba, N. C. Warner, D. J. O’Leary, R. H. Grubbs, Chem. Soc. Rev. 2018, 47, 4510.
[2] For a recent joint publication, see: V. César, Y. Zhang, W. Kośnik, A. Zieliński, A. A. Rajkiewicz, M. Ruamps, S. Bastin, N. Lugan, G. Lavigne, K. Grela, Chem. Eur. J. 2017, 23, 1950.
[3] For two reviews, see:  (a) Olefin Metathesis: Theory and Practice (Ed.: K. Grela), John Wiley and Sons, Hoboken, 2014; (b) ; L. Benhamou, E. Chardon, G. Lavigne, S. Bellemin-Laponnaz, V. César, Chem. Rev. 2011, 111, 2705.