A Pd-catalyzed highly regio- and stereoselective hydrocyanation was developed, providing a novel approach to the stereodivergent synthesis of β-cyano-substituted acrylates in good yields with a wide substrate scope. The judicious selection of ligands was crucial for elegant control over the stereodivergence. Furthermore, the success of the -hydrocyanation hinges on the right matching of Pd and , which not only ensured the catalytic activity but also prevented the formation of α-cyanation products.
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