State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, College of Chemistry, Nankai University , Tianjin 300071, China.
Center of Basic Molecular Science, Department of Chemistry, Tsinghua University , Beijing 100084, China.
J Org Chem. 2017 Apr 21;82(8):4129-4135. doi: 10.1021/acs.joc.7b00036. Epub 2017 Apr 3.
The recent discovery of the radical reactivity of a few traditionally electrophilic N-F reagents has sparked a renaissance of radical fluorination. A knowledge of the N-F bond dissociation enthalpies (BDE) of electrophilic N-F reagents is essential for understanding of their reactivities. However, a thorough literature survey revealed that such information is extremely sparse. This prompted us to carry out the first systematic computation on the N-F BDEs of electrophilic N-F reagents. The calculated N-F BDE scale of 88 electrophilic N-F reagents ranges from 49.3 to 80.0 kcal mol in acetonitrile. The large variety of N-F reagents and wide span of N-F BDEs make the scale a useful tool not only for the future rational design of novel reagents but also for judicious selection of appropriate ones to explore new radical fluorinations.
最近发现少数传统亲电 N-F 试剂具有自由基反应性，这引发了自由基氟化的复兴。了解亲电 N-F 试剂的 N-F 键离解焓 (BDE) 对于理解它们的反应性至关重要。然而，彻底的文献调查表明，此类信息极为稀缺。这促使我们对亲电 N-F 试剂的 N-F BDE 进行了首次系统计算。在乙腈中，计算得出的 88 种亲电 N-F 试剂的 N-F BDE 范围为 49.3 至 80.0 kcal/mol。N-F 试剂的种类繁多，N-F BDE 范围很广，因此该标度不仅是未来合理设计新型试剂的有用工具，也是明智选择合适试剂以探索新的自由基氟化反应的有用工具。
