Unifying Dearomatization and Rearomatization via Stereoselective Chlorination/Dechlorination: Resolution of Axially Chiral 1-Aryl-2-naphthols

We herein report a unified strategy integrating catalytic asymmetric chlorinative dearomatization and stereoselective dechlorinative rearomatization for resolving axially chiral 1-aryl-2-naphthols. By using a Sc(III)/Py-BOX catalytic system, naphthol-based biaryls underwent kinetic resolution through asymmetric chlorinative dearomatization. This process converted the intrinsic C(sp²)-C(sp²) axial chirality of one enantiomer into a conformationally favored C(sp²)-C(sp³) axis by generating a chlorine-containing C(sp³)-stereogenic center. The reaction showed high functional group tolerance and excellent enantioselectivities across a wide range of substrates. Subsequently, a stereospecific rearomatization protocol using triethylamine under blue-light irradiation was developed. This dechlorination method exploited an electron donor-acceptor (EDA) complex mechanism, efficiently converting the stored C(sp²)-C(sp³) axial chirality back to the original C(sp²)-C(sp²) axis, thus enabling full resolution of the biaryl atropisomers. The resolved 1-aryl-2-naphthols can be readily transformed into various catalytically and synthetically valuable molecules, such as axially chiral monophosphine, bisphosphine, aldehyde, and carboxylic acid.