Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University, Nanjing, 210037, China.
Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou, 350108, China.
Angew Chem Int Ed Engl. 2021 Dec 20;60(52):27271-27276. doi: 10.1002/anie.202112118. Epub 2021 Nov 18.
Radical fluorosulfonylation is emerging as an appealing approach for the synthesis of sulfonyl fluorides, which have widespread applications in many fields, in particular in the context of chemical biology and drug development. Here, we report the first investigation of FSO radical generation under electrochemical conditions, and the establishment of a new and facile approach for the synthesis of β-keto sulfonyl fluorides via oxo-fluorosulfonylation of alkynes with sulfuryl chlorofluoride as the radical precursor and air as the oxidant. This electrochemical protocol is amenable to access two different products (β-keto sulfonyl fluorides or α-chloro-β-keto sulfonyl fluorides) with the same reactants. The β-keto sulfonyl fluoride products can be utilized as useful building blocks in the synthesis of various derivatives and heterocycles, including the first synthesis of an oxathiazole dioxide compound. Furthermore, some β-keto sulfonyl fluorides and derivatives exhibited notably potent activities against Bursaphelenchus xylophilus and Colletotrichum gloeosporioides.
电化学条件下的 FSO 自由基生成研究及电化学氧化磺酰氟氯法构建β-酮基磺酰氟化合物
自由基氟磺酰化作为一种构建磺酰氟化合物的方法正逐渐兴起，磺酰氟化合物在许多领域都具有广泛的应用，尤其是在化学生物学和药物开发领域。在此，我们首次报道了电化学条件下 FSO 自由基的生成，并建立了一种新的简便方法，通过以磺酰氯氟为自由基前体、空气为氧化剂，实现了炔烃的氧-氟磺酰化反应，构建了β-酮基磺酰氟化合物。该电化学策略可利用相同的反应物来获得两种不同的产物（β-酮基磺酰氟或α-氯-β-酮基磺酰氟）。β-酮基磺酰氟产物可作为合成各种衍生物和杂环化合物的有用构建模块，包括首次合成了一个氧杂噻唑二酮化合物。此外，一些β-酮基磺酰氟化合物及其衍生物对松材线虫和胶孢炭疽菌表现出显著的活性。
