Tris(trimethylsilyl)silane as a Radical-Based Reducing Agent in Synthesis

Article abstract of DOI:10.1021/jo00002a035

Tris(trimethylsilyl)silane is an effective reducing agent for organic halides, selenides, xanthates, and isocyanides, as well as an effective hydrosilylating agent for dialkyl ketones and alkenes.The silane functions as a mediator in the formation of intermolecular carbon-carbon bonds via radicals and allows a variety of organic substrates to be used as alkyl radical precursors.Absolute rate constants for the reaction of (Me3Si)3Si^* radicals with a variety of organic compounds have been measured in solution by laser flash photolysis.At 294 K rate constants are >5 x 10⁷ M^-1 s^-1 for C=C double bonds that are activated by neighboring ?-electron systems or by electron-withdrawing groups.For other substrates, reactivities decreased in the order xanthate > selenide > isocyanide > nitro > sulfide.