Iridium-Catalyzed Intermolecular N—N Coupling for Hydrazide Synthesis Using <i>N</i>-Benzoyloxycarbamates as Acyl Nitrene Precursor
Fangfang Song, Shiyang Zhu, Hao Wang, Gong Chen
Abstract
An iridium-catalyzed intermolecular N-N coupling reaction using various N-benzoyloxyamides as acyl nitrene precursor for hydrazide synthesis has been developed. Unlike the carboxylic acid-derived dioxazolones used in previous report, this type of precursors allows the efficient synthesis of both acyl and oxycarbonyl substituted hydrazines from readily accessible precursors. Computational chemistry studies indicated that formation of the metal-acylnitrenoid intermediates via intramolecular hydrogen bond-assisted N-O cleavage may be the rate-determining step, and the subsequent nucleophilic attack of metal-acylnitrenoid by arylamines may be assisted by ClHN hydrogen bond to form the N-N bond.
Topics & Concepts
ChemistryNitreneIridiumHydrazideIntermolecular forceCatalysisCoupling (piping)Medicinal chemistryCombinatorial chemistryPolymer chemistryOrganic chemistryMoleculeEngineeringMechanical engineeringSynthesis and Catalytic ReactionsCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling Reactions