Palladium-Catalyzed Ortho-Silylation of Aryl Iodides with Concomitant Arylsilylation of Oxanorbornadiene: Accessing Functionalized (Z)-beta-Substituted Vinylsilanes and Their Analogues

A palladium-catalyzed ortho-silylation of aryl iodides/arylsilylation of oxanorbornadiene/retro-DielsAlder domino reaction was developed. Such a transformation provides access to various functionalized (Z)-beta-substituted vinylsilanes with exclusive selectivity using hexamethyldisilane as a bis-silylation reagent and 2,3-dicarbomethoxy-7-oxanorbornadiene (ONBD) as an ortho-C-H activator and ethylene surrogate. A variety of (Z)-beta-substituted vinylgermanes and (Z)-beta-substituted vinylstannanes were also obtained under mild reaction conditions. This atom-economical, stereoselective, and scalable approach is compatible with a diverse range of readily available functionalized aryl iodides.