摘要：Hubei Key Laboratory of Materials Chemistry and Service Failure; School of Chemistry and Chemical Engineering, Huazhong University

转自：康龙化成

Electrophilic (Hetero)Arene C−H Nitration by Ferric Nitrate Nonahydrate in Hexafluoroisopropanol

Yuzhu Zheng, Zongyi Liu, Zhaobo Ying, and Youwei Xie*

Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica; Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education;

Hubei Key Laboratory of Materials Chemistry and Service Failure; School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China;

—J. Org. Chem. 2025, DOI: 10.1021/acs.joc.5c00137

Recommended by Qilin Li_PDM

KEY WORDS:Nitration (反应类型),C(sp2)− N(成键类型), Arene (原料), Nitro arene (产物), HFIP, FeNO3 (其他)

ABSTRACT: In this article, we provide an extended substrate scope and more detailed mechanistic studies of an operationally simple and generally applicable arene nitration that we previously reported. This method utilizes safe and inexpensive Fe(NO3)3•9H2O as the nitro source in easily recyclable HFIP and obviates the need for corrosive acids (HNO3 + H2SO4). As a result, we speculated that it could serve as an effective substitute for the traditional mixed acid approach under most scenarios due to its operational simplicity. A general guidance for the application of this method was provided.

Background and this work

Nitration of aniline derivatives and highly electron-deficient substrates

Scale-up

In summary, Prof. Xie and coworkers describe an aromatic nitration with a nontoxic and inexpensive Fe(NO3)3•9H2O as a nitro source, facilitated by an easily recyclable solvent HFIP via a network of hydrogen-bond interactions. Compared to previously reported methods, this method does not require mixed acids or well designed nitro sources, and it is operationally facile that makes it suitable for a wide range of potential applications, including the late-stage modifications of highly functional natural products and drugs. They speculate that this protocol has the potential to replace the “mixed acid” approach to become the method of choice for synthetic organic chemists in the research laboratory. From a broader perspective, this study provides further information in understanding HFIP as well as in developing other milder, safer, and more atom-economic arene C−H functionalization.

来源：新浪财经