关键词: 硫酰氟, 芳基乙醇, 芳基乙烯, 碱性条件

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, V∶V=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