A four-step cascade reaction involving O[1, 3] sigmatropic shift and Smiles rearrangements as key steps. (29th April 2022)

• Record Type: Journal Article
• Authors: Zhang, Guangyu; Xu, Jiaxi
• Is Part Of: New journal of chemistry. Volume 46:Number 19(2022)
• Page Start: 9322
• Page End: 9330
• Publication Date: 2022-04-29
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/d2nj01393b
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : 4-Nitroaryl halides and N -acyl- N -arylhydroxyamines undergo cascade aromatic nucleophilic substitution- O [1, 3] sigmatropic shift-Smiles rearrangement-amide and ester exchange reaction, affording 2-((4-nitroaryl)amino)aryl carboxylates. Abstract : A new cascade aromatic nucleophilic substitution- O [1, 3] sigmatropic shift-Smiles rearrangement-amide and ester exchange reaction of 2/4-nitroaryl halides and N -acyl- N -arylhydroxylamines was observed and investigated in the presence of sodium hydride in THF, affording 2-((2/4-nitroaryl)amino)aryl carboxylate derivatives in low to excellent yields depending upon the electrophilicity of 2/4-nitroaryl halides. Generally, aryl halides with strong electron-withdrawing 2, 4, 6-trisubstituents gave the rearranged products in satisfactory to excellent yields. The current reaction provides not only an unprecedented cascade four-step reaction, but also a new strategy for the synthesis of 2-hydroxydiarylamine derivatives under transition metal-free conditions.