文献类型：期刊文献

英文题名：Radical-Chain Hydrosilylation of Alkenes Enabled by Triplet Energy Transfer

作者：Guo, Shixun[1,2];Wang, Wei[3,4];Zhang, Yongqiang[1,2]

机构：[1]Shanghai Frontiers Sci Ctr Optogenet Tech Cell Met, Shanghai Key Lab New Drug Design, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Pharm, Shanghai 200237, Peoples R China;[3]Univ Arizona, Dept Pharmacol & Toxicol, Tucson, AZ 85721 USA;[4]Univ Arizona, BIO5 Inst, Tucson, AZ 85721 USA

年份：2024

卷号：30

期号：52

外文期刊名：CHEMISTRY-A EUROPEAN JOURNAL

收录：;EI(收录号：20244017144446);WOS:【SCI-EXPANDED(收录号:WOS:001327309800027)，CCR-EXPANDED(收录号:WOS:001327309800027)】；

基金：Financial support from the program of the National Natural Science Foundation of China (22171080, Y.-Q. Z.) and Natural Science Foundation of Shanghai Municipality (23ZR1417200, Y.-Q. Z.) is gratefully acknowledged.

语种：英文

外文关键词：Radical-chain reaction; Hydrosilylation; Alkenes; Triplet energy transfer

摘要：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. A visible light-triggered organophotocatalytic hydrosilylation of alkenes and alkynes, which proceeds via a triplet energy transfer (EnT)-enabled radical chain pathway, has been developed. image