Cobalt-Catalyzed Z to E Isomerization of Alkenes: An Approach to (E)‑β-Substituted Styrenes

An efficient cobalt-catalyzed Z to E isomerization of β-substituted styrenes using the amido-diphosphine ligand was developed, delivering the (E)-isomers with good functional tolerance and high stereoselectivity. The reaction could be scaled up to gram-scale with a catalyst loading of 0.1 mol %, using a mixture of (Z)- and (E)-alkene as the starting material. Preliminary mechanistic studies indicated that cobalt­(I)-hydride and a benzylic-cobalt species were probably involved in the reaction, as supported by experiments and DFT calculations.