Synthesis of Z- or E-Trisubstituted Allylic Alcohols and Ethers by Kinetically Controlled Cross-Metathesis with a Ru Catechothiolate Complex.

The first examples of kinetically controlled cross-metathesis reactions that generate Z- or E-trisubstituted alkenes are disclosed. Transformations are catalyzed by ≤6.0 mol % of a Ru catechothiolate complex and afford trisubstituted allylic alcohols and ethers in up to 81% yield and >98% stereoisomeric purity. The method has considerable scope, as olefins containing an alcohol, an aldehyde, an epoxide, a carboxylic acid, or an alkenyl group may be used. Mechanistic models that account for the observed levels and trends in efficiency and stereochemical control are provided, based on DFT studies.