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

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

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

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