π‐Extended Silyl Enolates as Emerging Platforms in Radical Chemistry

π-Extended silyl polyenol ethers and their related silyl ketene acetals are well-established vinylogous nucleophiles in polar transformations; however, their potential in radical chemistry has only recently emerged. Owing to their intrinsically electron-rich character, arising from conjugated π-systems and σ-donating silyl groups, these substrates display unique reactivity under single-electron transfer conditions. This review provides a comprehensive overview of their behavior in radical-mediated processes, highlighting their versatile role as electron-rich SOMOphiles, radical precursors, and nucleophilic partners in radical–polar crossover manifolds. A key concept underlying their reactivity is the umpolung induced by single-electron oxidation, which converts nucleophilic vinylogous enolates into electrophilic radical cation or keto-allyl radical intermediates, thereby unlocking unconventional bond-forming pathways inaccessible through traditional two-electron chemistry. Moreover, these systems exhibit a distinctive propensity for remote functionalization at γ-, ε-, and η-positions, governed by electronic delocalization and radical stabilization across the extended π-framework. Recent advances in photoredox catalysis, electrochemistry, and transition metal-mediated methodologies have significantly expanded the scope and synthetic utility of these transformations, enabling efficient C─C and C─heteroatom bond formation, enantioselective variants, and applications in the synthesis of complex molecules. Collectively, these developments position π-extended silyl polyenol ethers as versatile and tunable platforms in modern radical chemistry.