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Mechanochemical Buchwald–Hartwig Cross-Coupling Reactions of Aromatic Primary Amines and Their Application to Two-Step One-Pot Rapid Synthesis of Unsymmetrical Triarylamines

Koji Kubota, Mahiro Takahashi, Francesco Puccetti, Hajime Ito

2025Organic Letters9 citationsDOI

Abstract

Herein, we report the development of the first general mechanochemical protocol for Buchwald-Hartwig cross-coupling using aromatic primary amines as nucleophiles. The mechanochemical arylamination reactions were rapid and completed within 30 min for most substrates, and all the synthetic operations were carried out in air. Notably, this mechanochemical approach effectively facilitated the arylamination of poorly soluble aryl halides, which are barely reactive in solution. In addition, we demonstrated that a two-step one-pot mechanochemical arylamination sequence enables the rapid, efficient, solvent-free, time-economical, and modular synthesis of various unsymmetrical triarylamines.

Topics & Concepts

ChemistryArylPrimary (astronomy)HalideCombinatorial chemistryNucleophileSolventCoupling reactionOne-pot synthesisNucleophilic aromatic substitutionOrganic chemistryNucleophilic substitutionCatalysisPhysicsAlkylAstronomyCatalytic Cross-Coupling ReactionsSynthesis and Reactivity of HeterocyclesOrganoboron and organosilicon chemistry