An electrochemical method for the decarboxylative silylation of α,β-unsaturated carboxylic acids was developed. A variety of alkenylsilanes could be obtained in satisfactory yields and excellent selectivities under external oxidant- and metal-free conditions. Mechanistic studies showed that the formation of the silyl radical was mediated by NHPI, which produces the hydrogen atom transfer (HAT) reagent phthalimide -oxyl (PINO) via multiple-site concerted proton-electron transfer (MS-CPET).
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