Hypervalent alkylsilicates represent practical, readily accessible precursors for alkyl radicals under photoredox conditions. The low oxidation potentials (E0 ~ +0.75 V vs SCE for primary silicates) and the innocuous byproducts generated upon oxidation make these hypervalent species ideal for a range of transformations. Alkyl radicals generated from alkylsilicates can be integrated into a dual catalytic manifold involving nickel which ultimately enables Csp3–C sp2 bonds to be forged under remarkably mild conditions. Additionally, these same radicals serve as effective hydrogen atom abstractors from thiols, furnishing thiyl radicals. These latter radicals can be funneled into a dual catalytic cross-coupling cycle to furnish thioethers. Further applications of alkylsilicates will be presented.

Alkylsilicates as versatile radical precursors in photoredox catalysis

252nd National Meeting (2016)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.