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March 10, 2026Angewandte Chemie0 citations

α‐Trifluoromethyl Substituted α‐Hydroxyhydrazides as Dianionic Ligands Enable Cu‐Catalyzed Aryl Amination With Higher Turnovers

JYJunying YeSouthern University of Science and Technology BGBin GuoSouthern University of Science and Technology RZRongxing ZhangSouthern University of Science and Technology

Key Points

The research aims to evaluate the efficiency of α-trifluoromethyl-substituted α-hydroxyhydrazides as ligands in copper-catalyzed reactions.
Synthesis of α-trifluoromethyl-substituted α-hydroxyhydrazides as ligands.
Evaluation of catalytic efficiency in coupling reactions with (hetero)aryl halides and amines.
Comparison of turnover rates under varying temperature and catalyst loading conditions.
Achieved complete conversion with 1 mol% catalyst for (hetero)aryl chlorides at 130°C.
Attained nearly 10,000 turnovers for (hetero)aryl bromides at 90°C with only 0.5 mol% catalyst.
Demonstrated applicability to primary and secondary amines with a variety of (hetero)aryl halides, yielding good to excellent results.

Abstract

ABSTRACT The α‐trifluoromethyl‐substituted α‐hydroxy‐hydrazides function as highly efficient ligands for copper‐catalyzed coupling reactions between (hetero)aryl halides (Cl, Br) and amines. With (hetero)aryl chlorides, only 1 mol% of the catalyst is required to achieve complete conversion at 130°C. For (hetero)aryl bromides, the reaction proceeds efficiently at room temperature with just 0.5 mol% catalyst loading and can reach nearly 10,000 turnovers when heated to 90°C. These turnover numbers represent the highest reported to date for copper‐catalyzed amination of (hetero)aryl halides (Cl, Br). The method is applicable to both primary and secondary amines, as well as a wide range of (hetero)aryl halides, delivering diverse (hetero)aryl amines in good to excellent yields.

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