Diastereoselective Synthesis of Dibenzoazepines through Chelation on Palladium(IV) Intermediates

Abstract

Joint palladium/norbornene organometallic catalysis allows for straightforward access to dibenzo­[<i>c,e</i>]­azepines. These synthetically challenging polycyclic frameworks form in one pot via a three-component coupling of an aryl iodide, a bromobenzylamine, and an olefin. A key, atroposelective aryl–aryl coupling from chelated Pd­(IV) intermediates dictates the outcome of the cascade. DFT modeling sheds light on the complex mechanism that allows the complete diasteroselectivity to be observed