Radical group transfer is a powerful tool for the formation of C–C bonds. These processes typically involve radical addition to C–C π bonds, followed by fragmentation of the cyclic intermediate. Despite the advantageous lability of organosilanes in this context, silicon-tethered radical acceptor groups have remained underexplored in radical group transfer reactions. We report a general photoredox-catalyzed protocol for the radical group transfer of vinyl and alkynyl silanes onto sp3 carbons, using activated and unactivated iodides as radical precursors. Our method displays high diastereoselectivity and excellent functional group tolerance. Mechanistic investigations revealed the key role played by silicon in facilitating a single-electron oxidation step, which leads to direct ring-opening and an overall redox-neutral process. This dataset contains raw files of proton nuclear magnetic resonance (1H NMR) and carbon nuclear magnetic resonance (13C NMR) of all compounds synthesized for and used in work: Radical group transfer of vinyl and alkynyl silanes driven by photoredox catalysis. The dataset is completed with raw files and analysis reports of correlated spectroscopy (COSY), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond correlation (HMBC), Fourier-transform infrared spectroscopy (FTIR) and high-resolution mass spectrometry (HRMS) of all new compounds synthesized for and used in this work.

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