Development of mild, robust and metal-free catalytic approach for the silyl transfer of silylboranes is critical to the advancement of modern organosilicon chemistry given their powerful capacity in the construction...

A visible-light-induced photocatalytic C–Si formation strategy has been disclosed by uncovering the reactivity of Martin’s spirosilane-derived pentacoordinate silylsilicates as silyl radical precursors. The hydrosilylation of a broad spectrum of alkenes and alkynes, as well as the C–H silylation of heteroarenes, has been demonstrated. Remarkably, Martin’s spirosilane was stable and could be recovered via a simple workup process. Furthermore, the reaction proceeded well using water as the solvent or low-energy green LEDs as an alternative energy source.