Flipping the Switch on Palladium-Catalyzed Carboiodination: Accessing Kinetic and Thermodynamic Products
Ramon Arora, Regina M. Oechsner, Clara Jans, Bijan Mirabi, Austin D. Marchese, Mark Lautens
Abstract
A palladium-catalyzed epimerization reaction of stereogenic alkyl iodides is reported. This transformation involves use of an air-stable precatalyst that efficiently epimerizes the C–I bond from the exo to the endo face of [2.2.1] bicyclic compounds. Mechanistic experiments support the stereoinversion of the C–I bond via reversible bond formation to generate the antiproduct bearing an endo iodide. Density functional theory studies were conducted to support a thermodynamically driven epimerization. Stoichiometric experiments suggested that irradiation of isolable alkyl–Pd(II) complexes promoted the C–I reductive elimination, which could even be applied to C–Br bond formation.