Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, China.
Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, Changzhou, 213164, China.
Angew Chem Int Ed Engl. 2020 Jul 6;59(28):11245-11249. doi: 10.1002/anie.201916727. Epub 2020 May 20.
Skeletal reorganization is a type of fascinating transformations owing to their intriguing mechanisms and utility in complex molecule synthesis. However, only a limited amount of examples are known for most functional groups. Herein, we describe such an unusual process of oxetanes. In the presence of In(OTf) as catalyst, oxetane-tethered anilines reacted unexpectedly to form 1,2-dihydroquinolines. This process not only provides expedient access to dihydroquinolines, but also represents a new reaction of oxetane. Mechanistically, it is believed that the reaction proceeds through initial nitrogen attack rather than arene attack followed by a series of bond cleavage and formation events. Control experiments provided important insights into the mechanism.
骨架重排是一种引人入胜的转化类型，其机制有趣，并可用于复杂分子的合成。然而，大多数官能团的例子数量有限。在此，我们描述了一种不寻常的氧杂环丁烷反应。在 In(OTf)3 作为催化剂的存在下，氧杂环丁烷键合苯胺出人意料地反应，形成 1,2-二氢喹啉。这个过程不仅为二氢喹啉的合成提供了一种简便的方法，而且代表了氧杂环丁烷的一种新反应。从机理上看，反应是通过初始氮原子的进攻而不是芳环的进攻，随后发生一系列键的断裂和形成反应。对照实验为反应机理提供了重要的见解。
