Facile ( <i>Z</i> )‐Selective Synthesis of β,γ‐Unsaturated Ketones by a Silicon‐based Olefination Strategy

A novel silicon-based olefination strategy to access challenging β,γ-(Z)-unsaturated ketones with high diastereoselectivity in a single step from easily accessible, branched vinyl silanes is presented. This new disconnection resolves many longstanding challenges that have prevented general and efficient synthetic approaches to (Z)-deconjugated enones, affording a broad scope of this type of alkenes with high functional group tolerance. The developed transformation has been applied as a key step in the synthesis of a range of natural products.