水为氧源电驱动烯烃合成四氢呋喃衍生物

doi:10.1016/S1872-2067(26)65178-9

催化学报 ›› 2026, Vol. 89: 177-183.DOI: 10.1016/S1872-2067(26)65178-9

水为氧源电驱动烯烃合成四氢呋喃衍生物

韩舒艳^a^,^*^,¹(), 张亚娟^a^,¹, 高艺轩^b, 李红芳^a, 贺燕燕^a, 贾振华^a^,^*(), 罗德平^a^,^c^,^*()

^a河南工业大学前沿交叉科学与技术学院,河南省分子耦合技术与应用重点实验室,河南郑州 450001,中国
^b中国农业科学院农业环境与可持续发展研究所,农业农村部农业与农村生态环境重点实验室, 农业清洁流域研究组,北京 100081,中国
^c南洋理工大学化学、化学工程与生物技术学院化学与生物化学系,新加坡

收稿日期:2026-03-03 接受日期:2026-05-18 出版日期:2026-10-18 发布日期:2026-09-01
通讯作者: *电子信箱: caist_hsy@haut.edu.cn (韩舒艳),
caist_zhjia@haut.edu.cn (贾振华),
teckpeng@ntu.edu.sg (罗德平).
作者简介:
¹共同第一作者.
基金资助:
河南省自然科学基金(252300423688);中国博士后科学基金会博士后资助计划(GZB20240202);河南工业大学(2023BS070);MTC个人研究资助(M21K2c0114);RIE2025 MTC项目(M22K9b0049)

Electrosynthesis of tetrahydrofurans from styrenes with water as oxygen source

Shuyan Han^a^,^*^,¹(), Yajuan Zhang^a^,¹, Yixuan Gao^b, Hongfang Li^a, Yanyan He^a, Zhenhua Jia^a^,^*(), Teck-Peng Loh^a^,^c^,^*()

^aHenan Linker Technology Key Laboratory, College of Advanced Interdisciplinary Science and Technology, Henan University of Technology, Zhengzhou 450001, Henan, China
^bAgricultural Clean Watershed Research Group, Institute of Environment and Sustainable Development in Agriculture, Chinese Academy of Agricultural Sciences, Key Laboratory of Agricultural and Rural Eco-Environment, Ministry of Agriculture and Rural Affairs, Beijing 100081, China
^cDivision of Chemistry and Biological Chemistry, School of Chemistry, Chemical Engineering, and Biotechnology, Nanyang Technological University, 21 Nanyang Link,Singapore 637371, Singapore

Received:2026-03-03 Accepted:2026-05-18 Online:2026-10-18 Published:2026-09-01
Contact: *E-mail:caist_hsy@haut.edu.cn(S. Han),caist_zhjia@haut.edu.cn(Z. Jia),teckpeng@ntu.edu.sg(T.-P. Loh).
About author:
¹ Contributed equally to this work.
Supported by:
Provincial Natural Science Foundation of Henan(252300423688);Postdoctoral Fellowship Program of CPSF(GZB20240202);Start-up Grant of Henan University of Technology(2023BS070);MTC Individual Research Grant(M21K2c0114);RIE2025 MTC Programmatic Fund(M22K9b0049)

摘要/Abstract

摘要：

四氢呋喃及其衍生物(THFs)作为一类重要的合成砌块, 广泛应用于有机合成和工业领域中. 烯烃的官能团氧化是构建该类化合物的代表性策略之一. 然而, 传统方法通常依赖于贵金属催化剂以及昂贵或存在安全隐患的含氧试剂(如环氧化合物、O₂等),严重制约了烯烃官能团转化策略在THFs合成中的实际应用. 因此, 发展基于非金属催化剂和安全氧源、具有广泛底物普适性和优异官能团兼容性的烯烃官能团转化方法,用于实现THFs的构建, 具有重要研究意义.

近年来, 以水为氧源的电催化转化, 为含氧化合物的绿色合成提供了新途径. 研究表明, 在阳极水氧化过程中原位生成的高活性氧中心中间体, 能够稳定存在于电极表面并选择性氧化有机底物. 鉴于此, 发展非金属催化的电合成策略, 以水为绿色氧源, 通过氧原子转移实现烯烃向THFs的高效转化, 具有重要的科学价值与应用前景. 然而, 目前相关研究仍鲜有报道, 该转化策略的实现仍面临诸多挑战. 本文首先通过机理分析, 推测反应可能经由烯烃衍生的自由基阳离子与羟基自由基(•OH)之间的自由基偶合途径进行, 其中烯烃衍生的自由基阳离子的生成是关键步骤. 为此, 我们对几种典型阳极材料的吸附能与功函进行了理论计算, 发现碳基材料对烯烃具有最强的吸附能力与氧化性, 可能更有利于烯烃衍生的自由基阳离子的生成. 后续实验结果验证了该推测, 证实碳材料在该反应中具有优越性. 进一步通过¹⁸O同位素标记实验确认了水作为反应氧源. 结合循环伏安测试与自由基捕获实验, 提出了可能的反应机理: 烯烃和水分子首先吸附于阳极碳材料表面, 分别失去电子生成相应的自由基阳离子与•OH; 二者发生自由基偶合形成中间体, 随后经脱质子化过程生成THFs. 随后, 采用廉价的碳纸作为阳极材料, 实现了系列高附加值THFs的合成, 证明该策略具有广泛的底物普适性与优异的官能团兼容性. 值得注意的是, 放大至克级规模的实验, 展现了该策略在合成高附加值THFs中的实际应用潜力.

综上, 本文以绿色安全的水为氧源, 采用非金属催化剂, 在温和条件下实现了烯烃化合物的高效高选择性转化,成功合成了系列高附加值THFs. 通过系统研究阐明了反应机制, 揭示了烯烃衍生的自由基阳离子与•OH的关键偶联过程. 该工作不仅为烯烃和水的协同高值化利用提供了新思路, 也为相关电合成反应的开发与应用奠定了理论与实验基础.

关键词: 电氧化, 非金属催化剂, 水为氧源, 氧转移, 烯烃的官能团氧化

Abstract:

Electrochemical synthesis offers a sustainable platform for redox transformations. However, many existing methods suffer from low Faradaic efficiency and high energy input. Herein, we report an efficient electrosynthetic strategy for the direct conversion of styrenes into tetrahydrofurans (THFs) using water as the sole oxygen source. By integrating experimental studies and theoretical calculations, we revealed that inexpensive carbon-based electrodes effectively promoted styrene activation and facilitated a radical-radical coupling of styrene-derived radical cations and hydroxyl radicals(•OH) generated in-situ from water oxidation. Moreover, key reactive intermediates were identified to support the proposed mechanism. This work established an efficient route to THFs and underscored the potential of electrochemical approaches for harnessing water as oxygen source in selective organic transformations.

Key words: Electrochemical oxidation, Non-metallic catalyst, Water as oxygen source, Oxygen transfer, Oxidation of functional groups in olefins

韩舒艳, 张亚娟, 高艺轩, 李红芳, 贺燕燕, 贾振华, 罗德平. 水为氧源电驱动烯烃合成四氢呋喃衍生物[J]. 催化学报, 2026, 89: 177-183.

Shuyan Han, Yajuan Zhang, Yixuan Gao, Hongfang Li, Yanyan He, Zhenhua Jia, Teck-Peng Loh. Electrosynthesis of tetrahydrofurans from styrenes with water as oxygen source[J]. Chinese Journal of Catalysis, 2026, 89: 177-183.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65178-9

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图/表 5

Fig. 1. (A) Representative THF-containing natural products and pharmaceuticals. (B) Direct oxygen transfer for oxygenation of organic molecules at the anode. (C) This work: electrosynthesis of THFs from styrenes with H2O as oxygen source.

Fig. 2. (A) Adsorption energies and (B) work function of styrene on graphite, Fe2O3, Co3O4 and NiO. (C) Electrosynthesis of 1b from 1a with H2O over different anode materials. (D) Transformations of 1b with H2O for 4 h under different current densities. (E) Time-dependent transformations of 1a with H2O. (F) Cycle-dependent performance of converting 1a into 1b (2 mA cm-2, 4h). All yields are 1H NMR yields (2,3,5-trichloropyridine as an internal standard).

Fig. 3. (A) CV curves of 1a on GC electrode with successive scans (10 cycles). 0.1 mmol 1a in 0.5 mol L-1 H2SO4/CH3CN (1:2 v/v, 3 mL, pH = 0.56, nH2SO4 = 0.5 mmol). (B) CV curves of GC in 0.1 mol L-1 n-Bu4NBF4 in CH3CN at a scan rate of 100 mV s-1 with and without 1a and/or H2O. (C) HR-MS of 1b obtained using H218O as oxygen source. (D,E) HR-MS data of key reaction intermediates trapped by DMPO during the electrosynthesis of 1b from 1a with H2O. (F) A proposed reaction mechanism.

Fig. 4. Substrate scope. aReaction conditions: undivided cell, CP as both anode and cathode, substrates (0.1 mmol), 0.5 mol L-1 H2SO4/CH3CN (1:2 v/v, 3 mL, pH = 0.56, nH2SO4 = 0.5 mmol), current density 2.0 mA cm-2, room temperature, in air. b Current density 3.0 mA cm-2, Ratios of stereoisomers (cis/trans) were determined by 1H NMR analysis. All yields are isolated yields. N.D. = not detected.

Fig. 5. (A) Gram-scale synthesis. (B) Schematic illustration. (C) voltage-time curves of the scale-up electrosynthesis of 1b from 1a with H2O in an undivided cell under constant current density at 2.0 mA cm-2 for 24 h.

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水为氧源电驱动烯烃合成四氢呋喃衍生物

Electrosynthesis of tetrahydrofurans from styrenes with water as oxygen source

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