Palladium-Catalyzed Gem-Diborylalkylation of Silyl Enol Ethers and N-Vinylacetamide via Diboryl Carbon-Centered Radicals.

Herein, a palladium-catalyzed coupling of gem-iododiborylalkanes with electron-rich olefins to access β,β-diboryl ketones and aldehydes under mild conditions is reported. This method exhibits broad substrate scope and excellent functional group tolerance. Mechanistic studies support a distinctive pathway involving gem-diboryl carbon-centered radicals and a Pd(0)/Pd(I) catalytic cycle, without the formation of Pd(II) intermediates. This protocol provides a new platform for accessing synthetically valuable gem-diboryl carbonyl compounds and expands the reactivity profile of organoboron-based radical transformations.