A versatile and highly Z -Selective olefin metathesis ruthenium catalyst based on a readily accessible N -heterocyclic carbene

A. Dumas (1) , R. Tarrieu (1) , T. Vives (1) , Thierry Roisnel (1) , V. Dorcet (1) , Olivier Baslé (1) , Marc Mauduit (1)

1 ISCR - Institut des Sciences Chimiques de Rennes

A ruthenium catalyst for Z-selective olefin metathesis has been synthesized from a readily accessible N-heterocyclic carbene (NHC) ligand that is prepared using an efficient, practical, and scalable multicomponent synthesis. The desired ruthenium complex with cyclometalated NHC ligand is obtained by means of selective C(sp3)-H activation at the adamantyl fragment and X-ray diffraction analysis unambiguously confirmed the structure of the precatalyst. The catalyst demonstrated attractive catalytic performance in self- and cross-metathesis at low catalyst loading to afford the desired internal olefins with high conversion and very high Z-selectivity (up to andgt;99%). The versatility of the chelated catalyst is illustrated by the high cis-selectivity (up to andgt;98%) and high tacticity control (up to andgt;98% syndiotactic) achieved in ring-opening polymerization, allowing for the production of highly microstructurally controlled norbornene-, norbornadiene-, and cyclopropene-derived polymers.

Mots clés: Z-selective catalyst; Ruthenium catalysts; Olefin metathesis; N-heterocyclic carbenes; N-heterocyclic carbene ligands; Ruthenium complexes; Catalyst selectivity; Activation analysis; Chelation; Ligands; Olefins; Ring opening polymerization; Ruthenium compounds; Synthesis (chemical); X ray diffraction analysis; Catalyst loadings; Catalytic performance; Multicomponent synthesis; Syndiotactic polymers; NHC ligand

Domaines: Catalyse; Chimie organique

A. Dumas, R. Tarrieu, T. Vives, Thierry Roisnel, V. Dorcet, et al.. A versatile and highly Z -Selective olefin metathesis ruthenium catalyst based on a readily accessible N -heterocyclic carbene. ACS Catalysis, 2018, 8 (4), pp.3257-3262. ⟨10.1021/acscatal.8b00151⟩. ⟨hal-01774411⟩