电驱动硫化学合成研究进展

doi:10.6023/cjoc202604034

摘要/Abstract

有机硫分子广泛出现于药物化学、功能材料、能源转移储存以及食品化学领域. 硫, 广泛的多价态(－2、0、＋2、＋4、＋6)赋予其独特的氧化还原特性, 令其合成高度依赖氧化还原的精准调控. 传统方法依赖过氧化物、高价碘等非绿色氧化剂, 存在原子经济性低、过度氧化、副产物污染等瓶颈. 电催化以电子为绿色氧化还原试剂, 通过电压、电流、电极、电解质精准调控电子转移速率与路径, 实现硫原子价态的精准调控转化, 兼具安全、高选择性与优异原子经济性. 此综述围绕电催化绿色氧化还原催化模式, 系统梳理电驱动硫化学的各类合成策略, 归纳总结相关研究进展, 并深入剖析其反应作用机制.

关键词: 硫化学, 电化学, 电氧化还原

Organic sulfur compounds are widely used in medicinal chemistry, functional materials, energy conversion and storage, and food chemistry. The unique multivalent redox properties of sulfur atoms (－2, 0, ＋2, ＋4, ＋6) make their synthesis highly dependent on precise redox regulation. Traditional methods rely on hazardous oxidants such as peroxides and hypervalent iodine, suffering from low atom economy, over-oxidation, and byproduct contamination. Electrocatalysis employs electrons as green redox reagents, enabling stepwise and controllable transformation of sulfur valence states by precisely regulating electron transfer rates and pathways through potential, current, electrodes, and media, offering a green, safe, highly selective, and atom-economical approach. This article focuses on the electrocatalytic green redox catalysis mode, systematically sorts out various synthetic strategies of electro-driven sulfur chemistry, summarizes the related research progress, and deeply analyzes its reaction mechanism.

Key words: sulfur chemistry, electrochemistry, electroredox

引用此文

张象金, 姜雪峰. 电驱动硫化学合成研究进展[J]. 有机化学, 2026, 46(9): 3448-3460.

Xiangjin Zhang, Xuefeng Jiang. Research Progress on Electro-Driven Sulfur Chemistry Synthesis[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3448-3460.

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图/表 18

图1. 硫化学的广泛应用

Figure 1. Wide applications of sulfur chemistry

图2. 电驱动硫化学合成策略

Figure 2. Electrochemically driven synthetic strategies for sulfur chemistry

图式1. 硫醚的电化学可控氧化合成亚砜与砜

Scheme 1. Electrochemically controlled oxidation of sulfides to sulfoxides and sulfones

图式2. 亚磺酸/硫醇的电氧化偶联合成硫代磺酸酯

Scheme 2. Electrochemical oxidative coupling of sulfinic acids and thiols to thiosulfonates

图式3. 硫醇与胺的电氧化偶联合成磺酰胺

Scheme 3. Electrochemical oxidative coupling of thiols with amines to form sulfonamides

图式4. 电氧化硫醚的α-氯代磺酰化反应及机理

Scheme 4. Electrochemical oxidative α-chlorosulfonylation of sulfides and its mechanism

图式5. 硫醚的电氧化氰亚胺化与亚磺酰亚胺化反应

Scheme 5. Electrochemical oxidative cyanoimidation and sulfoximidation of sulfides

图式6. 电还原镍催化硫醚合成反应体系

Scheme 6. Electroreductive nickel-catalyzed synthesis of sulfides

图式7. 亚砜的电还原脱氧制备硫醚

Scheme 7. Electrochemical reductive deoxygenation of sulfoxides to sulfides

图式8. 电还原镍催化磺酰氟合成反应体系

Scheme 8. Electroreductive nickel-catalyzed synthesis of sulfonyl fluorides

图式9. 硫醚的电还原精准脱氟官能化

Scheme 9. Electroreductive precise defluorination functionalization of sulfides

图式10. 电还原离子/自由基发散性构建二硫

Scheme 10. Electroreductive ionic/radical divergent construction of disulfides

图式11. 硫醇的电氧化交叉偶联合成非对称二硫

Scheme 11. Electrochemical oxidative cross-coupling of thiols to form unsymmetrical disulfides

图式12. 镍电催化构建二芳基硫醚

Scheme 12. Nickel-electrocatalyzed synthesis of diaryl sulfides

图式13. 电驱动多硫合成策略

Scheme 13. Electro-driven strategy for polysulfide synthesis

图式14. 硫醚的电氧化构建非对称二硫

Scheme 14. Electrochemical oxidative construction of unsymmetrical disulfide from sulfides

图式15. 电化学还原偶联构建硫醚反应体系

Scheme 15. Electrochemical construction of sulfides via reductive cross-coupling

图式16. 硫醚的电化学氘代甲基化

Scheme 16. Electrochemical trideuteromethylation of thioethers

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