Asymmetric Synthesis of Tetrahydrofurans with Vicinal Stereocenters by RhII/RuII Relay Catalysis.

CpRu-catalyzed asymmetric allylic alkylation serves as a versatile synthetic tool but remains underexplored. Herein, we report a relay system combining achiral Rh2(OAc)4 and a chiral pyridine-oxazoline-ligated Cp*Ru catalyst for asymmetric coupling of cinnamyl chlorides with diazo esters, generating silyl enol ethers in situ as key nucleophilic intermediates. This strategy affords chiral tetrahydrofuran derivatives with two vicinal stereocenters. Catalyst compatibility, excellent regioselectivity, and good enantioselectivity highlight its potential. Computational studies reveal the crucial role of Ru-centered chirality in reaction control.