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

Joint palladium/norbornene organometallic
catalysis allows for
straightforward access to dibenzo­[c,e]­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.