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. 2019 Mar 26;10(18):4775-4781.
doi: 10.1039/c9sc00595a. eCollection 2019 May 14.

Direct Conversion of Phenols Into Primary Anilines With Hydrazine Catalyzed by Palladium

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Free PMC article

Direct Conversion of Phenols Into Primary Anilines With Hydrazine Catalyzed by Palladium

Zihang Qiu et al. Chem Sci. .
Free PMC article

Abstract

Primary anilines are essential building blocks to synthesize various pharmaceuticals, agrochemicals, pigments, electronic materials, and others. To date, the syntheses of primary anilines mostly rely on the reduction of nitroarenes or the transition-metal-catalyzed Ullmann, Buchwald-Hartwig and Chan-Lam cross-coupling reactions with ammonia, in which non-renewable petroleum-based chemicals are typically used as feedstocks via multiple step syntheses. A long-standing scientific challenge is to synthesize various primary anilines directly from renewable sources. Herein, we report a general method to directly convert a broad range of phenols into the corresponding primary anilines with the cheap and widely available hydrazine as both amine and hydride sources with simple Pd/C as the catalyst.

Figures

Scheme 1
Scheme 1. Primary aniline synthesis.
Scheme 2
Scheme 2. Synthetic applications.
Scheme 3
Scheme 3. Studies of reaction mechanism.
Scheme 4
Scheme 4. Tentative mechanism.

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