Highly Active Chiral Ruthenium Catalysts for Asymmetric Ring-Closing Olefin Metathesis

The synthesis of olefin metathesis catalysts containing chiral, monodentate N-heterocyclic
carbenes and their application to asymmetric ring-closing metathesis (ARCM) are reported. These catalysts
retain the high levels of reactivity found in the related achiral variants (1a and 1b). Using the parent chiral
catalysts 2a and 2b and derivatives that contain steric bulk in the meta positions of the N-bound aryl rings
(catalysts 3−5), five- through seven-membered rings were formed in up to 92% ee. The addition of sodium
iodide to catalysts 2a−4a (to form 2b−4b in situ) caused a dramatic increase in enantioselectivity for many
substrates. Catalyst 5a, which gave high enantiomeric excesses for certain substrates without the addition
of NaI, could be used in loadings of ≤1 mol %. Mechanistic explanations for the large sodium iodide effect
as well as possible mechanistic pathways leading to the observed products are discussed.