Unifying Dearomatization and Rearomatization via Stereoselective Chlorination/Dechlorination: Resolution of Axially Chiral 1-Aryl-2-naphthols #MMPMID41353619
Zhang N; Chen Y; Qian G; Ge Y; Zhao D; Liu L; Bai L; Hong X; Liu J; Luan X
J Am Chem Soc 2025[Dec]; ? (?): ? PMID41353619show ga
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.
J+Am+Chem+Soc 2025 ; ? (?): ?
