Green and practical transition metal-free one-pot conversion of substituted benzoic acids to anilines using tosyl azide

Abstract

A simple and efficient method for conversion of 2-iodo/2-nitro benzoic acids and dihydropyranone-fused benzoic acids into corresponding anilines, using tosyl azide, under transition metal-free conditions was developed. Steric and electronic effects play crucial role.

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

“…An alternative approach to decarboxylative amination was presented by Ilangovan and colleagues (Scheme 79). [356] Tosylazide (TsN 3 ) was used as an easy‐to‐handle NH 2 source which promoted decarboxylation at low temperatures without a catalyst. Unfortunately, only 2‐iodo/2‐nitro benzoic acids and dihydropyranone fused benzoic acids are amenable substrates in this reaction.…”

Transition-Metal-Free Decarboxylative Amidation of Aryl α-Keto Acids with Diphenylphosphoryl Azide: New Avenue for the Preparation of Primary Aryl Amides

“…(a) Lei's work [7] (b) Xu's work [8] (c) Wang's work [9] (d) Yotphan's work [10] (e) IIangovan's work [11] O OH X R 6).…”

“…In addition, Ilangovan and co-workers reported a one-pot procedure for the conversion of 2-iodo/2-nitro benzoic acids into the corresponding anilines using tosyl azide as the nitrogen resource. And the substituent of 2-iodo or 2-nitro in benzoic acids is the necessary group for the success of this reaction [11] (Scheme 1, e).…”

Triple‐Bond Directed Csp2−N Bond Formation with N‐Fluorobenzenesulfonimide as Aminating Source: One‐Step Transformation of Aldehydes into Amines

“…In 2012, the Mainolfi group reported the synthesis of secondary anilines from substituted benzoic acid and amides by using a Cu catalyst at high temperature (Scheme a) . Later, Ilangovan and co‐workers synthesized primary anilines from substituted benzoic acid (Scheme b) . However, to our knowledge, no metal‐free synthesis of amines from aldehydes through in situ generated isocyanate intermediate has been explored to date (Figure ).…”

“…[9] Later,I langovan and co-workers synthesized primary anilines from substituted benzoic acid (Scheme 1b). [10] However, to our knowledge,n o metal-free synthesis of amines from aldehydes through in situ generated isocyanate intermediate has been explored to date ( Figure 1). Interestingly,i n2 012, Zhang and co-workers described a highly selectiveb enzylic CÀHa mination reactionb yc opper catalysis.…”