Oligosilanes as Silyl Radical Precursors through Oxidative Si-Si Bond Cleavage Using Redox Catalysis

Angew Chem Int Ed Engl. 2021 Jan 11;60(2):675-679. doi: 10.1002/anie.202011738. Epub 2020 Oct 29.

Abstract

Oligosilanes are of great interest in the fields of organic photonics and electronics. In this communication, a highly efficient visible-light-mediated hydrosilylation of electron-deficient alkenes through cleavage of a trimethylsilyl-polysilanyl Si-Si bond is explored. These reactions smoothly occur on readily available organo(tristrimethylsilyl)silanes and other oligosilanes in the presence of an IrIII -based photo-redox catalyst under visible light irradiation. Silyl radicals are generated through single electron oxidation of the oligosilane assisted by the solvent. The introduced method exhibits broad substrate scope and high functional group tolerance with respect to the organo(tristrimethylsilyl)silane and alkene components, enabling the construction of functionalized trisilanes. In addition, this catalytic system can be also applied to highly strained bicyclo[1.1.0]butanes as silyl radical acceptors.

Keywords: hydrosilylation; oligosilanes; photocatalysis; silyl radicals; single-electron transfer.