摘要
硫酰氟(SO_(2)F_(2))是众所周知的硫氟交换合成子,可参与多种官能团的相互转化.运用SO_(2)F_(2)实现芳基乙醇向芳基乙烯的转化,研究发现,该反应高效实用,反应条件为碱性,不需要昂贵的金属催化剂、配体或添加剂,官能团耐受性良好,收率72%~90%.并且该方法可成功实现4-苯基苯乙醇和2-萘苯乙醇的克级转化.推测可能的反应机理涉及醇类化合物串联的亲核取代-消除反应生成烯烃.
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(SO_(2)F_(2)),a widely recognized SuFEx synthon,mediates diverse functional-group interconversions.Here,we employ SO_(2)F_(2) 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 SO_(2)F_(2) 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 CH_(2)Cl_(2)(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 SO_(2)F_(2),furnishing a transient fluorosulfate.Rapid base-promoted elimination of fluorosulfinate then delivers the alkene product.
作者
冷静
谢承佳
郭双华
汤超
Leng Jing;Xie Chengjia;Guo Shuanghua;Tang Chao(School of Chemistry and Chemical Engineering,Yangzhou Polytechnic Institute,Yangzhou 225127)
出处
《化学学报》
北大核心
2025年第11期1335-1339,共5页
Acta Chimica Sinica
基金
2024年扬州工业职业技术学院“AI+”专业群专项教改课题(No.2024JGZX02)资助。
关键词
硫酰氟
芳基乙醇
芳基乙烯
碱性条件
sulfuryl fluoride
aryl ethanol
aryl ethylene
base condition
