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

Abstract

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.