Efficient and Highly Enantioselective Construction of Trifluoromethylated Quaternary Stereogenic Centers via High-Pressure Mediated Organocatalytic Conjugate Addition of Nitromethane to β,β-Disubstituted Enones

A very effective high-pressure-induced acceleration of asymmetric organocatalytic conjugate addition of nitromethane to sterically congested beta,beta-disubstituted beta-CF3 enones has been developed. A combination of pressure (810 kbar) and noncovalent catalysis with low-loading of chiral tertiary amine-thioureas (0.53 mol %) is shown to provide very efficient access to a wide range of gamma-nitroketones containing trifluoromethylated all-carbon quaternary stereogenic centers in the beta-position (8097%, 9298% ee).