Department of Chemistry, University of Texas at Austin, 100 East 24th Street, Austin, Texas 78712, United States.
Org Lett. 2022 Aug 12;24(31):5746-5750. doi: 10.1021/acs.orglett.2c02190. Epub 2022 Jul 29.
Herein we report the use of indoles, one of the most common nitrogen-containing heterocycles in FDA-approved drugs, as nucleophiles in the Pd-catalyzed aza-Wacker reaction. This -functionalization of indoles is a Markovnikov selective olefin functionalization of simple alkenes using catalytic Pd(NPhth)(PhCN) and O as the terminal oxidant in the presence of catalytic BuNBr. Various substituted indoles and alkenes are found to participate; 21 examples are presented with yields ranging from 41 to 97% isolated yield. Additionally, lactams and oxazolidinones are shown to participate under the reaction conditions. Mechanistic investigations suggest that the phthalimide ligand and BuNBr additive slow undesired side reactions: indole decomposition and olefin isomerization, respectively.
在此，我们报告了吲哚的应用，吲哚是 FDA 批准药物中最常见的含氮杂环之一，可作为钯催化的氮杂 Wacker 反应中的亲核试剂。这种吲哚的 - 官能团化是使用催化 Pd(NPhth)(PhCN)和 O 的 Markovnikov 选择性烯烃官能团化简单烯烃，在催化 BuNBr 的存在下作为末端氧化剂。发现各种取代的吲哚和烯烃都参与反应；提出了 21 个实例，产率范围为 41%至 97%（分离产率）。此外，在反应条件下还表明内酰胺和恶唑烷酮参与了反应。机理研究表明，邻苯二甲酰亚胺配体和 BuNBr 添加剂可分别减缓不需要的副反应：吲哚分解和烯烃异构化。
