Modular Synthesis of Fully‐Substituted and Configuration‐Defined Alkyl Vinyl Ethers Enabled by Dual‐Functional Copper Catalysis

Abstract Here we present a modular, chemo‐, regio‐, and stereoselective synthesis of fully‐substituted and configuration‐defined alkyl vinyl ethers (AVEs) using simple chemical feedstocks. The distinctive approach involves the chemo‐ and regioselective functionalization of the CF 2 unit in gem ‐difluorinated cyclopropanes with O−H and C−H nucleophiles in a specific order. The resulting highly functionalized cyclopropanyl ethers then undergo a stereoselective ring‐opening process to produce fully‐substituted and configuration‐defined AVEs. These AVEs are rarely accessible through conventional methods and are easily transformable. Mechanistic experiments indicate that the success of this method relies on the use of dual‐functional copper catalysis, which is involved in both the functionalization of the CF 2 unit and the subsequent ring‐opening process.