Asymmetric catalysis stands as a core domain in modern organic synthesis and catalysis science, wherein the design and innovation of chiral ligands represent the decisive driving force for breakthroughs. Benefiting from their rigid structures and outstanding chiral induction capability, spirocyclic scaffolds have become privileged platforms for chiral ligand development. In recent years, silicon-stereogenic spirocyclic frameworks have emerged as a new frontier in chiral ligand design, owing to the larger atomic radius, longer C-Si bonds, unique electronic effects, and distinct spatial configurations of silicon. This review systematically summarizes the developmental history of chiral silicon-centered spirocyclic scaffolds, with a focus on the synthetic strategies for two privileged cores, SPSiOL and SPOSiOL. The structural features and design philosophies of diverse silicon-spiro ligands, including diphosphines, bisphosphites, bisoxazolines, and phosphine-oxazolines, are comprehensively discussed. Their applications in Rh-, Ni-, Pd-, Cu-, and Ir-catalyzed asymmetric hydrogenation, hydrosilylation, hydroboration, cycloisomerization, [2+2+2] cycloaddition, and intramolecular alkynylamination are thoroughly overviewed. This review aims to provide a systematic reference for the rational design of novel chiral silicon-spiro ligands, mechanistic investigations, and synthetic applications, thereby promoting the advancement of chiral silicon chemistry in pharmaceuticals and materials.

Key words: asymmetric catalysis, chiral spiro ligands, silicon-spiro skeleton, chiral silicon chemistry, transition metal catalysis