An efficient method for the synthesis of gem-silylboronate esters based on transition-metal-free reaction of arylboronic acids and trimethylsilyldiazomethane is developed, and Suzuki–Miyaura cross-coupling of gem-silylboronate esters with aryliodides is described.

A transition‐metal‐free method for the alkylation of gem‐diborylalkanes with α,β‐unsaturated ketones has been developed. It is demonstrated that the α‐boryl radicals can be generated efficiently from gem‐diborylalkanes with the aid of catechol and oxidants. The α‐boryl radicals formed through such process can be engaged in conjugate addition reaction with α,β‐unsaturated ketones. This transformation is a straightforward method for the synthesis of γ‐borylketones.