Aminocarbonylation of (Hetero)aryl Bromides with Ammonia and Amines using a Palladium/DalPhos Catalyst System

Variants of the DalPhos [2-aminophenylbisadamantyl)phosphine] ligand family were examined in a palladium-catalyzed carbonylative amination reaction using inexpensive carbon monoxide and ammonia as reagents. As a result of this survey, the Pyr-DalPhos ligand was identified as being effective for the selective aminocarbonylation of aryl bromides with ammonia, as well as primary and secondary alkylamines. A variety of primary aromatic, heteroaromatic and N-substituted benzamides were formed in moderate to good yields. As part of this study, a (Mor-DalPhos)Pd-benzoyl complex was prepared and crystallographically characterized, thereby showing the viability of the carbonyl insertion step.