Chiral Arylthiol-Catalyzed Asymmetric Hydrodifluoroalkylation of Alkenes Facilitated by Noncovalent Interaction

Herein, a photodriven enantioselective hydrodifluoroalkylation of methyleneindanes with α-bromodifluoroamides catalyzed by a <i>C</i>₂-symmetric chiral arylthiol was developed. This protocol delivers chiral <i>gem</i>-difluorinated indane-derived amides in good to excellent yields with high enantioselectivities.

Mechanistic investigation reveals that the <i>gem</i>-dimethyl substituent in the substrate is critical to amplify the free energy difference between diastereomeric HA transition states, while a π–π interaction between the substrate <i>N</i>-phenyl group and the arylthiol catalyst benzylic substituent underpins the enantiocontrol.