Unifying Dearomatization and Rearomatization via Stereoselective Chlorination/Dechlorination: Resolution of Axially...

Area of Science:

• Organic Chemistry
• Asymmetric Synthesis
• Chiral Molecules

Background:

• Axially chiral biaryls, such as 1-aryl-2-naphthols, are important structural motifs.
• Efficient methods for resolving these atropisomers are crucial for synthetic applications.

Purpose of the Study:

• To develop a unified strategy for the kinetic resolution of axially chiral 1-aryl-2-naphthols.
• To enable the transformation of these resolved compounds into valuable chiral building blocks.

Main Methods:

• Catalytic asymmetric chlorinative dearomatization using a Sc(III)/Py-BOX system.
• Kinetic resolution of naphthol-based biaryls via dearomatization.
• Stereoselective dechlorinative rearomatization using triethylamine and blue-light irradiation.

Main Results:

• High functional group tolerance and excellent enantioselectivities were achieved during dearomatization.
• A stereospecific rearomatization protocol efficiently restored the axial chirality.
• The method allows for the full resolution of biaryl atropisomers.

Conclusions:

• The developed strategy provides a versatile approach for resolving axially chiral 1-aryl-2-naphthols.
• Resolved naphthols serve as precursors for diverse catalytically and synthetically important molecules.
• This work expands the toolkit for accessing enantiomerically pure axially chiral compounds.