银催化吲哚的脱芳基三氟甲氧基化反应

Silver-Enabled Dearomative Trifluoromethoxylation of Indoles.

作者信息

Deng Zhijie, Meng Lingduan, Bing Xiao, Niu Shaoxiong, Zhang Xiaofeng, Peng Junqin, Luan Yu-Xin, Chen Li, Tang Pingping

机构信息

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.

College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China.

出版信息

J Am Chem Soc. 2024 Jan 31;146(4):2325-2332. doi: 10.1021/jacs.3c11653. Epub 2024 Jan 17.

DOI:10.1021/jacs.3c11653

PMID:38232384

Abstract

The only known method for the dearomative trifluoromethoxylation of indoles is preliminary, with only one substrate successfully undergoing the reaction. In this study, we not only developed a broadly applicable method for indole dearomative trifluoromethoxylation but also achieved divergent trifluoromethoxylation by fine-tuning the reaction conditions. Under optimized conditions, with a silver salt and an easily handled OCF reagent, various indoles smoothly underwent dearomatization to afford a diverse array of ditrifluoromethoxylated indolines in 50-84% isolated yields with up to 37:1 diastereoselectivity, and fluorinated trifluoromethoxylated indolines were obtained with exclusive selectivity. In addition, the reaction conditions were compatible with other heteroaromatic rings as well as styrene moieties.

摘要

已知的吲哚去芳构化三氟甲氧基化的唯一方法还处于初步阶段，仅有一个底物成功进行了该反应。在本研究中，我们不仅开发了一种广泛适用的吲哚去芳构化三氟甲氧基化方法，还通过微调反应条件实现了多样化的三氟甲氧基化。在优化条件下，使用银盐和易于操作的OCF试剂，各种吲哚顺利发生去芳构化反应，以50 - 84%的分离产率得到了一系列多样的双三氟甲氧基化吲哚啉，非对映选择性高达37:1，并且以专一的选择性得到了氟化三氟甲氧基化吲哚啉。此外，该反应条件与其他杂芳环以及苯乙烯部分兼容。