Xu Fan, Zhu Lin, Zhu Shaobin, Yan Xiaomei, Xu Hai-Chao
The Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China) http://chem.xmu.edu.cn/kydw_ktz/hcxu/index.html.
Chemistry. 2014 Sep 26;20(40):12740-4. doi: 10.1002/chem.201404078. Epub 2014 Aug 21.
An electrochemical approach to the intramolecular aminooxygenation of unactivated alkenes has been developed. This process is based on the addition of nitrogen-centered radicals, generated through electrochemical oxidation, to alkenes followed by trapping of the cyclized radical intermediate with 2,2,6,6-tetramethylpiperidine-N-oxyl radical (TEMPO). Difunctionalization of a variety of alkenes with easily available carbamates/amides and TEMPO affords aminooxygenation products in high yields and with excellent trans selectivity for cyclic systems (d.r. up to>20:1). The approach provides a much-needed complementary route to existing cis-selective methods.
已开发出一种用于未活化烯烃分子内氨氧化的电化学方法。该过程基于通过电化学氧化产生的氮中心自由基加成到烯烃上，随后用2,2,6,6-四甲基哌啶-N-氧基自由基（TEMPO）捕获环化自由基中间体。各种烯烃与易于获得的氨基甲酸酯/酰胺和TEMPO进行双官能化反应，可高产率地得到氨氧化产物，并且对于环状体系具有出色的反式选择性（d.r.高达>20:1）。该方法为现有的顺式选择性方法提供了急需的补充途径。
