文献类型：期刊文献

英文题名：Anionic Fries Rearrangement of ortho-Iodophenyl Carboxylate Initiated by Potassium Hydride

作者：Zhou, Yuxin[1];He, Mengyang[1];Yi, Tingting[1];Chen, Xiaobei[3,4];Wang, Mengqing[1];Liu, Xuejun[2];Chen, Xiaodong[2];Zhang, Shilei[1];Hu, Yanwei[1]

机构：[1]Soochow Univ, Coll Pharmaceut Sci, Jiangsu Key Lab Drug Discovery & Translat Res Brai, Suzhou 215123, Jiangsu, Peoples R China;[2]Shanghai Neutan Pharmaceut Co Ltd, Shanghai 201315, Peoples R China;[3]East China Univ Sci & Technol, Sch Pharm, State Key Lab Bioreactor Engn, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Sch Pharm, Shanghai Key Lab New Drug Design, Shanghai 200237, Peoples R China

年份：2025

卷号：27

期号：20

起止页码：5293

外文期刊名：ORGANIC LETTERS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001489069800001)，CCR-EXPANDED(收录号:WOS:001489069800001)】；

基金：This work was supported by the National Natural Science Foundation of China (22271206 and 22071053), PAPD (a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions), and Suzhou International Joint Laboratory for Diagnosis and Treatment of Brain Diseases.

语种：英文

摘要：In order to generate an aryl anion, metal-halogen exchanges initiated by alkyllithium, lithium amide, or Grignard reagent are frequently employed. However, carbonyl groups are not compatible with these reagents. Herein, we demonstrate that aryl iodide can undergo direct K-I exchange with KH to produce an aryl anion species. Due to the toleration of this process with ester and ketone groups, it is suitable for the anionic Fries rearrangement reaction of ortho-iodophenyl carboxylates to provide ortho-acylphenol or ortho-acylaniline products, which has long been a great challenge for traditional methods. Moreover, our protocol can be used for cascade reactions to prepare xanthone and acridone. Notably, although K-I exchange is the major reaction pathway of our process, it is accompanied by hydrodehalogenation (Pierre's process) as a side reaction, which has been validated by the identification of phenol in the final reaction mixture.