Sequential Ni-Catalyzed Cross-Coupling and Ru-Catalyzed Isomerization of E/Z Alkenyl Ethers: A Stereoconvergent Route to Allylsilanes

A stereoconvergent one-pot protocol for converting E/Z mixtures of alkenyl ethers into stereodefined allylsilanes has been developed by merging Ni-catalyzed cross-coupling and Ru-catalyzed alkene isomerization. Optimization of each catalytic step identified Ni(OAc)2/TMEDA and RuHCl(CO)(PPh3)3 as effective components. The method exhibits high E-selectivity, broad substrate scope, and good functional group tolerance. This strategy offers a practical solution to longstanding challenges in stereoselective synthesis from stereochemically mixed precursors.