A ruthenium catalyst for Z-selective olefin metathesis has been synthesized from a readily accessible N-heterocyclic carbene (NHC) ligand that is prepared thanks to an efficient, practical and scalable multicomponent synthesis. The desired ruthenium complex with cyclometalated NHC ligand is obtained by means of selective C(sp 3)-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 >99%). The versatility of the chelated catalyst is illustrated by the high cis-selectivity (up to >98%) and high tacticity control (up to >98% syndiotactic) achieved in ring-opening-polymerization, allowing for the production of highly microstructurally controlled norbornene, norbornadiene and cyclopropene-derived polymers.

A new multicomponent procedure was applied to the synthesis of (a)chiral bulky unsymmetrical unsaturated 2,6-diisopropylphenyl-N-heterocyclic carbene (NHC) precursors with excellent selectivity (up to 95%) and good yields. This approach offers access to new chiral NHCs ligands, which found successful applications in both copper-catalyzed asymmetric allylic alkylation and coppercatalyzed asymmetric borylation.