Naichen Zhang, Yuyang Chen, Gan-Lu Qian, Yicong Ge, Dongwei Zhao, Long Liu, Lu Bai, Xin Hong, Jingjing Liu, Xinjun Luan
High Resolution Image Download MS PowerPoint Slide 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(sp 2 )–C(sp 2 ) axial chirality of one enantiomer into a conformationally favored C(sp 2 )–C(sp 3 ) axis by generating a chlorine-containing C(sp 3 )-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(sp 2 )–C(sp 3 ) axial chirality back to the original C(sp 2 )–C(sp 2 ) 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.