State Key Laboratory of Elemento-organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), 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 Aug 18;82(16):8697-8702. doi: 10.1021/acs.joc.7b01771. Epub 2017 Aug 3.
The recent recognition of the novel application of a few traditional electrophilic trifluoromethylthiolating reagents as SCF radical sources offers a remarkable new opportunity for the development of radical trifluoromethylthiolation reactions. Herein, the first trifluoromethylthio radical donating ability (TtDA) scale of electrophilic SCF-transfer reagents has been developed. This scale is based on Y-SCF bond dissociation energies, which were obtained by density functional calculations (M06-2X). Single electron transfer is revealed to exhibit a substantial Y-SCF bond-weakening effect, thus significantly facilitating the SCF radical (SCF) release. The results may aid in future novel radical SCF-transfer reagent design and new reaction development.
最近，人们认识到一些新型亲电三氟甲基硫代试剂可作为 SCF 自由基源，这为开发自由基三氟甲基硫代反应提供了一个显著的新机会。在此，开发了第一个亲电 SCF 转移试剂的三氟甲基硫自由基给体能力（TtDA）尺度。该尺度基于通过密度泛函计算（M06-2X）获得的 Y-SCF 键离解能。单电子转移显示出对 Y-SCF 键的显著弱化效应，从而显著促进了 SCF 自由基（SCF）的释放。这些结果可能有助于未来新型自由基 SCF 转移试剂的设计和新反应的开发。
