Acid‐Catalyzed Synthesis of <i>Si</i> ‐Stereogenic Silanes

Comprehensive Summary The importance of Si ‐stereogenic silanes has been recognized in many fields of chemical science. Consequently, numerous catalytic enantioselective methods for their synthesis have been developed. Despite these advances, such methods have traditionally relied on transition‐metal catalysts, predominantly rhodium and palladium. Recently, Brønsted acid catalysts have emerged as powerful alternatives to transition‐metal catalysts. In particular, imidodiphosphorimidate (IDPi) and chiral phosphoric acid (CPA) catalysts have enabled access to structurally diverse Si ‐stereogenic silanes, including silyl ethers, silacycles, and disiloxanes, that were not previously attainable. In this review, we describe the recent advances made in Brønsted acid catalysis for the synthesis of Si ‐stereogenic silanes. We also discuss the relevant background and reaction mechanisms. We hope that this review will suggest future research directions in this emerging area. Key Scientists