Radical-Chain Hydrosilylation of Alkenes Enabled by Triplet Energy Transfer

Development of mild, robust and metal-free catalytic approach for the hydrosilylation of alkenes is critical to the advancement of modern organosilicon chemistry given their powerful capacity in the construction of various C−Si bonds. Herein, we wish to disclose a visible light-triggered organophotocatalytic strategy, which proceeds via a triplet energy transfer (EnT)-enabled radical chain pathway. Notably, this redox-neutral protocol is capable of accommodating a broad spectrum of electron-deficient and -rich alkenes with excellent functional group compatibility. Electron-deficient alkenes are more reactive and the reaction could be finished within a couple of minutes even in PBS solution with extremely low concentration, which suggests its click-like potential in organic synthesis. The preparative power of the transformations has been further highlighted in a number of complex settings, including the late-stage functionalization and scale-up experiments. Furthermore, although only highly reactive (TMS)₃SiH is suitable hydrosilane substrate, our studies revealed the great reactivity and versatility of (TMS)₃Si− group in diverse C−Si and Si−Si bond cleavage-based transformations, enabling the rapid introduction of diverse functional groups and the facile construction of valuable quaternary silicon architectures.