Abstract: | 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. |