Rapid and Modular Access to Vinyl Cyclopropanes Enabled by Air‐stable Palladium(I) Dimer Catalysis

While vinyl cyclopropanes are valuable functional groups in drugs or natural products as well as established precursors to trigger a rich variety of synthetic transformations, their reactive nature can make their installation via direct catalytic approaches challenging. We herein present a modular access to (di)vinyl cyclopropanes under very mild conditions and full conservation of stereochemistry, allowing access to the cis or trans cyclopropane‐ as well as E or Z vinyl‐stereochemical relationships. Our protocol relies on air‐stable dinuclear Pd(I) catalysis, which enables rapid (<30 min) and selective access to a diverse range of vinyl cyclopropane motifs at room temperature, even on gram scale.