Organocatalytic Atroposelective Arylation: A Practical Strategy for the Synthesis of Axially Chiral Compounds

As important structural scaffolds prevalent in natural products, bioactive molecules, pharmaceuticals, and functional materials, axially chiral compounds have contributed significantly to the fields of drug discovery, materials science, and asymmetric catalysis. In recent years, conceptual strategies such as direct axis formation, de novo arene construction, and functionalization of prochiral or racemic biaryls have spurred extensive research into the catalytic asymmetric synthesis of axial chirality. Among these, organocatalytic atroposelective arylation reactions, which enable the construction of a stereogenic axis in a single step under environmentally friendly, metal‐free conditions, have demonstrated profound synthetic potential across diverse methodologies. This review systematically summarizes the seminal contributions and methodological developments in this field, with particular emphasis on the use of various electrophilic arylation reagents under catalyst control for the asymmetric synthesis of enantioenriched biaryl, heterobiaryl, and nonbiaryl atropisomers featuring diverse structures and well‐defined conformational properties. Mechanistic insights are comprehensively discussed, along with the strengths and limitations. Furthermore, critical perspectives on future directions are provided, highlighting opportunities for further methodological innovation in scientific research and broader applications in industrial organic synthesis. We hope that the repertoire of organocatalytic atroposelective arylation reactions will continue to flourish and inspire chemists worldwide to further advance this evolving field.