Chiral Atropisomeric‐NHC Catechodithiolate Ruthenium Complexes for Z ‐Selective Asymmetric Ring‐Opening Cross Metathesis of Exo ‐Norbornenes

International audience; A set of 16 chiral ruthenium complexes containing atropisomerically stable N-Heterocyclic Carbene (NHC) ligands was synthesized from prochiral NHC precursors. After a rapid screening in asymmetric ring-opening-cross metathesis (AROCM), the most effective chiral atrop BIAN-NHC Ru-catalyst (up to 97:3 er) was then converted to a Z-selective catechodithiolate complex. The latter proved to be highly efficient in Z-selective AROCM of exo-norbornenes affording valuable trans-cyclopentanes with excellent Z-selectivity (>98%) and high enantioselectivity (up to 96.5:3.5 er).