Transition-Metal-Free Intramolecular <i>N</i>-Arylations

<i>N</i>-Substituted phenoxazines and related aza analogs have been prepared from <i>N</i>-acetylated aryloxy anilides by transition-metal-free, base-catalyzed cyclization reactions. In the presence of a mixture of 10 mol % of <i>N,N</i>′-dimethylethylenediamine (DMEDA) and 2 equiv of K₂CO₃ in toluene at 135 °C the products are obtained in high yields

A Mild, Ferrocene-Catalyzed C–H Imidation of (Hetero)Arenes

A simple method for direct C–H imidation is reported using a new perester-based self-immolating reagent and a base-metal catalyst. The succinimide products obtained can be easily deprotected <i>in situ</i> (if desired) to reveal the corresponding anilines directly. The scope of the reaction is broad, the conditions are extremely mild, and the reaction is tolerant of oxidizable and acid-labile functionality, multiple heteroatoms, and aryl iodides. Mechanistic studies indicate that ferrocene (Cp₂Fe) plays the role of an electron shuttle in the decomposition of the perester reagent, delivering a succinimidyl radical ready to add to an aromatic system