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

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