Organocatalytic, Oxidative, Intermolecular Amination and Hydrazination of Simple Arenes at Ambient Temperature

Abstract

New atom-economical, environmental friendly, direct oxidative intermolecular processes of amination and hydrazination of nonprefunctionalized arenes were developed. The products were formed in a good regioselective manner under organocatalytic conditions at ambient temperature.

Metal-Catalyzed and Metal-Free Intermolecular Amination of Light Alkanes and Benzenes

“…Organocatalytic versions have been subsequently pursued 75 in amidations of simple arenes by N -methoxybenzamide and hydrazinations by N -(1,3-dioxoisoindolin-2-yl)acetamide (Scheme 27(a)). Key to the success of these processes is the development of a protocol that uses aryl iodides in catalytic amounts, and relies on sacrificial peracetic acid, along with trifluoroacetic acid, to generate the oxidant in situ.…”

Oxidative Heterocycle Formation Using Hypervalent Iodine(III) Reagents

“…To this end, Antonchick and coworkers [103] disclosed a highly efficient intermolecular process for the introduction of an amine or hydrazine functionality into simple non-prefunctionalized arenes. The method was successfully utilized in the hydrazination of several heterocyclic compounds and biologically active molecules (Scheme 38).…”

Metal‐Free Oxidative Carbon‐Heteroatom Bond Formation Through C–H Bond Functionalization

“…Unfortunately, all of these methods required stoichiometric amounts of hypervalent iodine reagent, so further development was necessary for an organocatalytic version under mild conditions. Subsequently, an organocatalytic direct oxidative intermolecular process involving monoamination and hydrazination of nonprefunctionalized arenes at ambient temperature in the presence of the aryl iodide 2,2′‐diiodo‐4,4′,6,6′‐tetramethyl‐1,1′‐biphenyl ( 3 ) as organocatalyst (Scheme ) has very recently been developed 21. This method was utilized for simple arenes and for late‐stage functionalization of biologically active molecules.…”