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0 25120401

DOI: https://doi.org/10.6023/A25120401

研究通讯

电化学芳基乙烯硫羟基化反应合成β-羟基硫醚及其抗菌活性

  • 韩中艳 ,
  • 陈梅梅 ,
  • 张驰 ,
  • 薛伟 ,
  • 谷利军
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  • 贵州大学 绿色农药全国重点实验室, 精细化工研究开发中心 贵阳 550025

收稿日期: 2025-12-08

  网络出版日期: 2026-01-21

基金资助

贵州省科技计划项目(黔科合基础-ZK-[2024]一般086); 贵州大学科研启动项目([(2023)5)]).

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Electrochemistry-Enabled Hydroxysulfurization of Aryl Alkenes for the Synthesis of β-Hydroxysulfides and Their Antifungal Ativities

  • Han Zhong-Yan ,
  • Chen Mei-Mei ,
  • Zhang Chi ,
  • Xue Wei ,
  • Gu Li-Jun
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  • State Key Laboratory of Green Pesticide, Center for R&D of Fine Chemicals of Guizhou University, Guiyang 550025

Received date: 2025-12-08

  Online published: 2026-01-21

Supported by

Guizhou Provincial Basic Research Program (Natural Science) (No. QianKeHeJiChuZK [2024]YiBan086) and the starting grant of Guizhou University [(2023)5)].

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摘要

β-羟基硫醚是许多药物及天然产物分子的重要结构单元. 该类化合物具有抗菌、抗炎、抗肿瘤及抗-HIV等活性, 还是一种重要的有机合成中间体, 发展高效、绿色的合成方法构建β-羟基硫醚具有重要意义. 以廉价易得的芳基乙烯和三甲基硅基硫醚为原料, 镁棒和碳棒做阳极及阴极, 在无分隔电解瓶中, 电催化条件下, 室温下一步实现芳基乙烯的硫羟基化反应, 高收率地合成了系列β-羟基硫醚. 该反应条件温和, 原子经济性高, 底物范围广, 避免了氧化剂、过渡金属催化剂及恶臭硫酚的使用. 在合成的基础上, 采用菌丝生长速率法测试了目标化合物β-羟基硫醚的体外抗真菌活性. 部分化合物在浓度为100 μg/mL时, 对水稻纹枯病菌、蓝莓灰霉病菌表现出较好的体外抑制活性, 优于对照药剂嘧菌酯.

关键词： 电催化; 芳基乙烯; 硫羟基化; β-羟基硫醚; 抗菌活性

本文引用格式

韩中艳 , 陈梅梅 , 张驰 , 薛伟 , 谷利军 . 电化学芳基乙烯硫羟基化反应合成β-羟基硫醚及其抗菌活性[J]. 化学学报, 0 : 25120401 . DOI: 10.6023/A25120401

Abstract

As the core skeleton structure of many drugs and natural products, β-hydroxysulfides exhibit a variety of biological activities, including anti-fungal, anti-tumor, anti-inflammatory, and anti-HIV properties. They are also used as synthetic building blocks. Complementary catalytic methods that facilitate the efficient synthesis of structurally diverse β-hydroxysulfides are highly sought after. Herein, a mild and efficient electricity-driven strategy has been developed for the synthesis of β-hydroxysulfides from aryl alkenes and trimethylsilyl sulfides in an undivided cell with Mg anode and graphite cathode, while exhibiting mild conditions, high atom-economy, and excellent functional group tolerance. The reaction avoids the use of transition-metal catalysts, peroxide reagents, and malodorous thiols. A representative procedure is described as follows. A mixture of styrene (28.3 mg, 0.2 mmol), (phenylthio)trimethylsilane (58.9 mg, 0.3 mmol), and nBu4NBF4 (65.8 mg, 0.2 mmol) in acetonitrile (8 mL) and acetic acid (1 mL) was added to a three-necked flask (10 mL). The electrolysis was performed in an undivided cell equipped with a Mg rod anode (Ø = 6 mm) and a graphite rod cathode (Ø = 6 mm) under a constant current of 16 mA (~20.4 mA/cm²) at room temperature for 4 h. After completion, the mixture was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous Na₂SO₄, filtered, and concentrated. The crude product was purified by silica gel column chromatography to afford the target compound. Based on the synthesis, the antifungal activities of the target compounds, β-hydroxysulfides, was tested using the mycelial growth rate method in vitro. With the commercial fungicide Azoxystrobin (Azo) as the positive control, the antifungal activities of the target compounds against two plant pathogenic fungi, Rhizoctonia solani (R.s.) and Botrytis cinerea (B.c.), were determined at a concentration of 100 μg/mL. Notably, some compounds showed higher inhibition rates against the tested fungi than the control agent Azoxystrobin. Among them, at a concentration of 100 μg/mL, compound (3ae) exhibited inhibition rates of 90% and 97% against R.s. and B.c., respectively. which were superior to those of the control agent Azoxystrobin (72% and 74%, respectively). Finally, a preliminary exploration was conducted on the relationship between the antifungal activities of the target compounds and their molecular structures, providing valuable insights for the future development of more efficient agricultural antifungal agents.

Key words： electrochemical catalysis; aryl alkenes; thiohydroxylation; β-hydroxysulfide; antifungal activity

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