Thermo-Promoted Reactions of Anthranils with Carboxylic Acids, Amines, Phenols, and Malononitrile under Catalyst-Free Conditions

Abstract

A convenient and atom-economical procedure for the thermo-promoted reactions of anthranil with different substrates was developed. The catalyst-free process affords various useful building blocks with good to moderate yields. This chemistry enables several step- and cost-effective approaches for biologically interesting molecules and provides an efficient platform for the investigation of untapped reactions at high temperature.

Copper‐Catalyzed Acylhalogenation of 3‐Methylanthranils with Acid Halides: Synthesis of N‐(2‐(2‐Haloyl)phenyl)amides

“…Based on these outcomes and previous works, [8,16,17] a tentative mechanism is proposed in Scheme 4. First, benzoyl chloride is attacked by 1 a to form intermediate A , which was detected by high resolution mass spectroscopy in this reaction system [8a,c,f] . An oxidative addition of copper(I) to the N−O bond affords intermediate B [16] .…”

Synthesis of Active Hexafluoroisopropyl Benzoates via a Multicomponent Reaction

“…However, synthetic methods for anthranilic acid ester from anthranils remain rare. To the best of our knowledge, the Zhang group reported the first example via a reactive ketene intermediate in 2019 (Scheme b) . Unfortunately, this transformation required very high temperature and the yield is low.…”

“…To the best of our knowledge, the Zhang group reported the first example via a reactive ketene intermediate in 2019 (Scheme 1b). 2 Unfortunately, this transformation required very high temperature and the yield is low. Esters, especially the active esters, are highly attractive building blocks.…”

Anthranils: versatile building blocks in the construction of C–N bonds and N-heterocycles

“…In 2019, Zhang and coworker disclosed a series of nucleophilic additions of the in situ-generated ketene intermediates from anthranils (Scheme 35). 42 In this reaction, various commonly used nucleophiles proved to be suitable substrates. For example, anilines and phenols were verified as good reaction partners Scheme 31 Metal-free annulation of acetophenones and anthranils for the synthesis of functionalized quinolines.…”