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Updated: Mar 3, 2026

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Published on: January 19, 2016

α-トリフルオロメチル置換α-ヒドロキシヒドラジドをジアニオン性配位子として用い、より高いターンオーバーを可能にする銅触媒によるアリールアミノ化

Junying Ye¹, Bin Guo¹, Rongxing Zhang¹

¹Shenzhen Key Laboratory of Cross-Coupling Reactions & Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, China.

Angewandte Chemie (International ed. in English)

|March 2, 2026

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.

キーワード:

(ヘテロ)アリールハライドアリールアミノ化銅触媒カップリング反応 α-トリフルオロメチル置換α-ヒドロキシヒドラジド配位子

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