Electrochemical C–H silylation of azauracils with hydrosilanes

• Justification for the submission to Molecular Catalysis. • Late-stage functionalization of bioactive molecule derivatives. • Simple and green conditions. • Broad FG tolerance & scale-up. • Absence of metal/oxidant & high atom economy. Polysubstituted azauracils represent highly important nitrogen-containing heterocyclic compounds that are widely found in biologically active molecules. Current synthetic methods primarily rely on expensive transition metals or often toxic photocatalysts to achieve C H functionalization of azauracils, making it imperative to develop simpler and more practical synthetic approaches. Electroorganic synthesis offers an excellent alternative strategy. Herein, we disclose an electrochemical C H silylation method for the synthesis of various silicon-substituted azauracils using azauracils and hydrosilanes as starting materials. This transformation is conducted in an undivided cell, offering operational simplicity, excellent substrate compatibility, and scalability to gram-scale synthesis. Furthermore, this strategy enables the late-stage derivatization of valuable molecules. Mechanistic studies reveal that azauracils capture silicon radicals through three distinct pathways, ultimately generating diverse polysubstituted azauracil derivatives.