Visible‐Light‐Catalyzed CSi Bond Cleavage: Reaction Strategies and Research Advances

Over the past decade, visible‐light photoredox catalysis has emerged as a powerful and sustainable platform for generating radical intermediates, enabling novel bond‐forming strategies under mild conditions. Organosilanes, due to their stability, accessibility, and tunable reactivity, have become versatile radical precursors through photoinduced oxidative CSi bond cleavage. This review provides the first systematic summary of recent advances in visible‐light‐promoted CSi bond cleavage, covering not only established photoredox and metal/photoredox synergistic catalysis but also emerging strategies such as photoinduced small‐molecule catalysis and photoinduced metal complex catalytic systems. This review also highlights two challenges that are currently under‐researched: the cleavage of nonactivated C( sp 3 )Si bonds and the selective CH functionalization of silanes. By focusing on catalyst design, this review analyzes how photosensitizer structure, metal–ligand environments, and chiral control units govern reaction efficiency and selectivity. Mechanistic insights and future directions are discussed, with the aim of inspiring the development of novel catalytic systems for sustainable synthesis and precision molecular editing.