Hypervalent Iodine‐Promoted Aromatization of Exocyclic β‐Enaminones for the Synthesis of meta ‐ N , N ‐Diarylaminophenols

A metal‐ and additive‐free milder cascade approach for the synthesis of meta ‐ N , N ‐diarylaminophenols (DAAP) starting from exocyclic β‐enaminones has been developed. The feasibility of the process is rationalized by the suitable molecular geometry of β‐enaminones for tandem N ‐arylative α‐iodination and aromatization under milder basic conditions. Furthermore, the developed strategy has been extended to the synthesis of meta ‐ N ‐benzyl‐ N ‐arylaminophenols (BAAP). 4‐Ethylpropionyl‐2‐cyclohexenone has been explored to give 7‐diarylaminochroman‐2‐one (DAAC) by employing a similar one‐pot approach. The plausible mechanistic steps were deduced based upon isolation of a stable intermediate and structural identification through X‐ray crystallographic analysis.