Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (11): 1335-1339.DOI: 10.6023/A25060213 Previous Articles     Next Articles

Article

硫酰氟介导下芳基乙醇向芳基乙烯的转化

冷静*(), 谢承佳, 郭双华, 汤超   

  1. 扬州工业职业技术学院 化学工程学院 扬州 225127
  • 投稿日期:2025-06-11 发布日期:2025-12-03
  • 通讯作者: 冷静
  • 基金资助:
    项目受2024年扬州工业职业技术学院“AI+”专业群专项教改课题(2024JGZX02)

Transformation of Aryl Ethanol to Aryl Ethylene Mediated by Sulfuryl Fluoride

Leng Jing*(), Xie Chengjia, Guo Shuanghua, Tang Chao   

  1. School of Chemistry and Chemical Engineering, Yangzhou Polytechnic Institute, Yangzhou 225127
  • Received:2025-06-11 Published:2025-12-03
  • Contact: Leng Jing
  • Supported by:
    Specialized Teaching Reform Project on the “AI+” Major Cluster of Yangzhou Polytechnic in 2024(2024JGZX02)

Sulfur-fluoride exchange (SuFEx) click chemistry, introduced in 2014, has rapidly evolved into a powerful synthetic platform. Centered on sulfonyl fluoride reactivity, it enables the swift and efficient construction of sulfonylated scaffolds. Owing to their unique electrophilic character, sulfonyl fluorides have found broad utility in organic synthesis, chemical biology, drug discovery and advanced materials. Recent years have witnessed SuFEx not only driving the preparation of hypervalent sulfur-fluorine compounds but also delivering promising antitumor, antibacterial and antioxidant agents with markedly improved bioactivity. Drawing upon the design of small-molecule S-F building blocks, the authors provide a comprehensive overview of recent advances in sulfonyl fluoride synthesis. As pivotal intermediates, these compounds are poised to catalyze progress across chemistry, materials science and biomedicine. Sulfuryl fluoride (SO2F2), a widely recognized SuFEx synthon, mediates diverse functional-group interconversions. Here, we employ SO2F2 to transform aryl ethanols into aryl ethylenes practicably and efficiently under basic conditions that dispense with expensive metals, ligands or additives. Broad functional-group tolerance is observed and yields range from 72% to 90%. After screening organic and inorganic bases in both identity and stoichiometry, together with temperature, we settled on the following protocol. To a 25 mL sealed tube are charged phenethyl alcohol (1.0 mmol), t-BuOK (5.0 equiv.) and anhydrous dimethyl sulfoxide (DMSO) (5 mL). The vessel is then purged and maintained under a slight positive pressure of SO2F2 delivered from a balloon via syringe needle. The mixture is stirred at 60 ℃ for 12 h. Work-up consists of dilution with water (10 mL), extraction with CH2Cl2 (10 mL×3), washing the combined organic layers with brine, drying over Na2SO4, concentration, and purification by flash column chromatography (EtOAc/petroleum ether, VV=1∶20) to afford the desired styrene. The method accommodates twelve electronically and sterically varied styrenes and has been scaled to gram quantities for 4-phenylphenethyl alcohol and 2-naphthylethanol. The proposed mechanism proceeds via tandem nucleophilic substitution-elimination: deprotonation of the alcohol generates an alkoxide that attacks the electrophilic sulfur of SO2F2, furnishing a transient fluorosulfate. Rapid base-promoted elimination of fluorosulfinate then delivers the alkene product.

Key words: sulfuryl fluoride, aryl ethanol, aryl ethylene, base condition