Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers , Hunan University of Science and Technology , Xiangtan 411201 , P. R. China.
J Org Chem. 2019 Jul 19;84(14):9044-9050. doi: 10.1021/acs.joc.9b00965. Epub 2019 Jul 10.
Thioethers are converted to thiocyanates via fluorium-initiated dealkylative cyanation. Selectfluor is used as the oxidant, and trimethylsilyl cyanide is used as the cyanation reagent. The well-streamlined procedure is user-friendly, operationally simple, and step-economical. The current mechanistic studies show that the sulfur radical cation and cyano radical are both involved. They combine to deliver cyanosulfonium, an intermediate toward thiocyanate after dealkylation. Alternatively, a nucleophilic mechanism is also possible. Our dealkyaltive cyanation is also efficient in synthesizing thiocyanates with strongly electrophilic functionalities.
硫醚可通过氟引发的脱烷基化氰化作用转化为硫氰酸盐。使用 Selectfluor 作为氧化剂，三甲基硅基氰化物作为氰化试剂。该流水线式程序操作简便、经济性好、用户友好。目前的机理研究表明，硫自由基阳离子和氰基自由基都参与了反应。它们结合生成氰硫鎓离子，这是脱烷基化后生成硫氰酸盐的中间体。另一种可能的机制是亲核机制。我们的脱烷基化氰化反应在合成具有强亲电官能团的硫氰酸盐时也很有效。
