Isothiourea‐Catalysed Acylative Kinetic Resolution of Aryl–Alkenyl (sp(2) vs. sp(2)) Substituted Secondary Alcohols

The non‐enzymatic acylative kinetic resolution of challenging aryl–alkenyl (sp(2) vs. sp(2)) substituted secondary alcohols is described, with effective enantiodiscrimination achieved using the isothiourea organocatalyst HyperBTM (1 mol %) and isobutyric anhydride. The kinetic resolution of a wide range of aryl–alkenyl substituted alcohols has been evaluated, with either electron‐rich or naphthyl aryl substituents in combination with an unsubstituted vinyl substituent providing the highest selectivity (S=2–1980). The use of this protocol for the gram‐scale (2.5 g) kinetic resolution of a model aryl–vinyl (sp(2) vs. sp(2)) substituted secondary alcohol is demonstrated, giving access to >1 g of each of the product enantiomers both in 99:1 e.r.