Martin’s spirosilane and Martin’s silicates: synthesis and synthetic applications

Martin's spirosilane provides a versatile molecular platform for studying the unique reactivity of hypercoordinated silicon derivatives. Its high Lewis acidity, strong interactions with fluorine-and oxygen-based Lewis sites and ability to adopt pentacoordination offer an unusual balance between stability and reactivity. In this illustrated review, we highlight the wide range of applications made possible by Martin's ligand-derived silicon compounds, which encompass anion recognition, Lewis acid-base chemistry, group-transfer reactions, stereochemical control, bond activation, and the manipulation of Si-Si bonds. Particular attention is given to the generation and transfer of or alkyl, alkynyl, fluorinated, and silicon-based groups, as well as to the use of Martin's silicates as precursors for carbon-centered radicals under photoredox conditions. The compatibility of these silicon-based systems with catalytic approaches, such as photocatalysis and nickel catalysis, demonstrates the synthetic versatility of this platform. Beyond their direct chemical reactivity, these compounds demonstrate how the hypercoordination of silicon can be exploited to influence molecular geometry, electronic structure, and bond reactivity. Overall, Martin's spirosilane leverages hypercoordination to control molecular reactivity and enables selective, efficient, and more sustainable synthetic chemistry.