Ir(iii)-Catalyzed site-selective amidation of azoxybenzenes and late-stage transformation

Abstract

An efficient site-selective C–H amidation of azoxybenzenes with 1,4,2-dioxazol-5-ones by Ir catalysis has been established for the diversification of azoxybenzenes.

Sustainable Amidation Reactions – Recent Advances

“…H. Li and co‐workers reported the use of azoxybenzene 42 as substrate and 1,4,2‐dioxazol‐5‐ones to afford several ortho ‐aminated derivatives 44 via Ir(III)‐catalysis (Scheme ).…”

“…Synthesis of ortho ‐aminated derivatives from azoxybenzene and 1,4,2‐dioxazol‐5‐ones via Ir(III)‐catalysis …”

Recent Progress in the C−N Bond Formation via High‐Valent Group 9 Cp*M(III)‐Catalyzed Directed sp2 C−H Activation

“…The synthetic route proceeds through C−H amidation followed by cyclization under redox neutral conditions, leaving only CO 2 and H 2 O as the byproducts (Scheme 44a). Later, Li et al [48b] . developed a strategy involving C−H amidation of azoxybenzenes 132 with dioxazolones 7 using the Ir(III)‐catalyst (Scheme 44b).…”

Synthesis of Unsymmetrical Aromatic Azoxy Compounds by Silver‐Mediated Oxidative Coupling of Aromatic Amines with Nitrosoarenes

“…To introduce different functional groups into azoxy compounds, much effort has been directed toward the C−H functionalization of symmetrical azoxyarenes, with o rtho ‐acylation, halogenation, acetoxylation, alkoxylation,, sulfonamidation, acylamidation, and alkenylation achieved to form unsymmetrical azoxyarenes. Unfortunately, these reactions suffer from the severe drawback that functional groups can only be introduced in the ortho ‐position of the synthesized azoxybenzenes, which limits the scope of functionality.…”