AbstractReadily available, sterically, and electronically tunable sulfonamides have been developed as effective photoinduced hydrogen atom transfer (HAT) catalysts for selective Si−H functionalizations of a broad range of silanes. N‐centered radicals, catalytically generated from sulfonamides by photoredox catalyzed single‐electron oxidation, are the key intermediates that enable an effective HAT process for silyl radical generation to achieve hydrosilylation of activated alkenes. Additionally, this catalytic system can also be applied for the activation of Ge−H bond for hydrogermylation of activated alkenes through hydrogen atom transfer by sulfonamide derived nitrogen centered radical. The ability to generate silyl and germyl radical using this photochemical HAT process offers new avenue towards the sustainable synthesis of organosilicon and organogermanium compounds.
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