Iridium‐Catalyzed Dehydrogenative Aromatization of Cyclohexanols and Cyclohexanones to Phenols

Comprehensive Summary Catalytic dehydrogenative aromatization (CDA) has emerged as a powerful strategy for the synthesis of substituted phenols. However, most of the known CDA methods suffer from limited functional group compatibility due to the use of strong oxidants, reductants, or bases. Herein, we report a ( cis ‐P 2 Cl)Ir‐catalyzed CDA reaction enabled by transfer dehydrogenation (TD). This catalytic system is effective for CDA of both cyclohexanone and cyclohexanol derivatives and demonstrates excellent tolerance toward a variety of functional groups, including readily oxidizable electron‐rich heterocycles. DFT studies further reveal that the ( cis ‐P 2 Cl)Ir catalyst is thermodynamically disfavored for the formation of a potential out‐of‐cycle catalyst species, iridium phenoxyl hydride complex, via oxidative addition of the phenol O–H bond, thereby preventing catalyst inhibition observed in the previously reported TD system.