College of Chemistry and Molecular Sciences, The Institute for Advanced Studies (IAS), Wuhan University, Wuhan, 430072, Hubei, P.R., China.
National Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang, 330022, Jiangxi, P.R., China.
Angew Chem Int Ed Engl. 2016 Jan 18;55(3):1094-7. doi: 10.1002/anie.201508729. Epub 2015 Dec 4.
Controlling selectivity is of central importance to radical chemistry. However, the highly reactive and unstable radical intermediates make this task especially challenging. Herein, a strategy for taming radical redox reactions has been developed, in which solvent-bonding can alter the reactivity of the generated radical intermediates and thereby drastically alter the reaction selectivity at room temperature. Various β-oxy sulfoxides and β-hydroxy sulfides can be facilely obtained, some of which are difficult to synthesize by existing methods. Notably, neither a metal catalyst nor any further additives are necessary in these processes.
控制选择性对于自由基化学至关重要。然而，高反应性和不稳定性的自由基中间体使得这一任务极具挑战性。在此，开发了一种控制自由基氧化还原反应的策略，其中溶剂键合可以改变生成的自由基中间体的反应性，从而在室温下剧烈改变反应选择性。各种β-氧基砜和β-羟基硫醚可以很容易地获得，其中一些用现有方法难以合成。值得注意的是，这些过程既不需要金属催化剂也不需要任何进一步的添加剂。
