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Light‐Promoted C–N Coupling of Aryl Halides with Nitroarenes

Gang Li, Liu Yang, Jianjun Liu, Wei Zhang, Rui Cao, Chao Wang, Zun‐Ting Zhang, Jianliang Xiao, Dong Xue

2020Angewandte Chemie International Edition150 citationsDOI

Abstract

Abstract A photochemical C–N coupling of aryl halides with nitroarenes is demonstrated for the first time. Catalyzed by a Ni II complex in the absence of any external photosensitizer, readily available nitroarenes undergo coupling with a variety of aryl halides, providing a step‐economic extension to the widely used Buchwald–Hartwig C–N coupling reaction. The method tolerates coupling partners with steric‐congestion and functional groups sensitive to bases and nucleophiles. Mechanistic studies suggest that the reaction proceeds via the addition of an aryl radical, generated from a Ni I /Ni III cycle, to a nitrosoarene intermediate.

Topics & Concepts

HalideArylChemistrySteric effectsNucleophilePhotochemistryCoupling (piping)Coupling reactionCombinatorial chemistryCatalysisMedicinal chemistryOrganic chemistryMaterials scienceMetallurgyAlkylSulfur-Based Synthesis TechniquesRadical Photochemical ReactionsCatalytic Cross-Coupling Reactions
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