M[TPP]Cl (M = Fe or Mn)-Catalyzed Oxidative Amination of Phenols by Primary and Secondary Anilines

Abstract

Iron- and manganese-catalyzed para -selective oxidative amination of (4-R)phenols by primary and secondary anilines was developed. Depending on the identity of the R group, the products of this efficient reaction are either benzoquinone anils (C–N coupling) that are produced via a sequential oxidative amination/dehydrogenation (R = H), oxidative amination/elimination (R = OMe) steps, or N , O -biaryl compounds (C–C coupling) that are formed when R = alkyl through an oxidative amination/[3,3]-sigmatropic rearrangement (quinamine rearrangement) process.

A Voltammetric pH Sensor for Food and Biological Matrices

“…The formation of an intense purple color confirmed the IAd formation. Reported spectra were compatible with those available in the literature, obtained through a different synthetic pathway [54].…”

A voltammetric pH sensor for food and biological matrices

“…Newly synthesized compound was characterized by 1 Reported spectra were compatible with those available in the literature, obtained through a different synthetic pathway [54].…”

Mechanistic Insights into the FeCl3-Catalyzed Oxidative Cross-Coupling of Phenols with 2-Aminonaphthalenes

“…9f , 10 Lately, our group has developed an M[TPP]Cl (M = Fe or Mn, TPP = 5,10,15,20-tetraphenyl-21H,23H-porphine)-catalyzed para -selective oxidative amination of phenols by primary and secondary anilines ( Scheme 1 B). 11 We have demonstrated that, depending on the identity of the phenolic para -R group, the products of this coupling are either benzoquinone anils (when R = H or OMe) or N , O -biaryl compounds (when R = alkyl). In a previous paper, we developed a two-step synthesis of optically pure NOBIN derivatives.…”

“…5b However, the partial order for the phenolic component is no longer zero when the catalyst has a limited number of vacant sites, as exemplified by Katsuki [(Fe[μ-OH][salen]) 2 catalyst] 13 and Pappo [Fe[phosphate] 3 catalyst] ( Figure 1 B). 5c Furthermore, when the reaction is mediated by Fe[TPP]Cl, which has only a single axial position available for binding, the coupling takes place between a ligated phenoxyl radical and a liberated phenoxyl 5a or an anilino radical 11 by an outer-sphere radical–radical coupling mechanism ( Figure 1 C). These studies show that the coupling mechanism changes as a function of the iron coordination sphere.…”