硫空位促进硝基芳烃与芳基醛电化学还原偶联高选择性电合成亚胺

doi:10.1016/S1872-2067(24)60115-4

催化学报 ›› 2024, Vol. 65: 206-216.DOI: 10.1016/S1872-2067(24)60115-4

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硫空位促进硝基芳烃与芳基醛电化学还原偶联高选择性电合成亚胺

谢典科^a^,¹, 杨天仪^a^,¹, 马重阳^a^,¹, 董崇礼^b, 王双印^a, 邹雨芹^a^,^*()

^a湖南大学化学化工学院, 先进催化教育部工程研究中心, 化学生物传感与计量学国家重点实验室, 湖南长沙410082
^b淡江大学物理系, 台湾新北25137

收稿日期:2024-06-18 接受日期:2024-08-05 出版日期:2024-10-18 发布日期:2024-10-15
通讯作者: *电子信箱: yuqin_zou@hnu.edu.cn (邹雨芹).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2020YFA0710000);国家自然科学基金(22122901);国家自然科学基金(22425021);湖南省自然科学基金(2021JC0008);湖南省自然科学基金(2021RC3054)

Highly selective electrosynthesis of imines via electroreduction coupling of nitroarenes with aryl aldehydes on Co₉S₈ with positively charged sulfur vacancies

Dianke Xie^a^,¹, Tianyi Yang^a^,¹, Chongyang Ma^a^,¹, Chung-Li Dong^b, Shuangyin Wang^a, Yuqin Zou^a^,^*()

^aState Key Laboratory of Chemo/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education, Hunan University, Changsha 410082, Hunan, China
^bDepartment of Physics, Tamkang University, New Taipei City 25137, Taiwan, China

Received:2024-06-18 Accepted:2024-08-05 Online:2024-10-18 Published:2024-10-15
Contact: *E-mail: yuqin_zou@hnu.edu.cn (Y. Zou).
About author:¹ These authors contribute equally to this work.
Supported by:
National Key R&D Program of China(2020YFA0710000);National Natural Science Foundation of China(22122901);National Natural Science Foundation of China(22425021);Provincial Natural Science Foundation of Hunan(2021JC0008);Provincial Natural Science Foundation of Hunan(2021RC3054)

摘要/Abstract

摘要：

亚胺是一类具有碳氮双键(C=N)的有机化合物, 是合成化学中重要的反应物和中间体, 广泛应用于药品、农用化学品和其他精细化学品等生物活性化合物的合成. 从硝基苯合成功能化亚胺在现代合成化学中具有重要意义. 然而, 传统的亚胺合成方法通常需要使用氢气和大量芳香族化合物溶剂, 这会导致能源损耗和环境污染, 因此, 需要开发更加先进绿色的合成策略. 近年来, 电化学硝基苯还原反应因其过程可持续、效率高、反应条件温和等特点而备受关注. 研究人员将硝基化合物与羰基化合物结合, 生成了硝酮和亚胺等更多有价值的C-N偶联产物. 由于竞争反应(如硝基苯的自偶联和苯甲醛的还原)的发生和可逆的希夫碱缩合过程限制了亚胺的收率, 实现高收率的电催化合成亚胺仍然是一个挑战. 因此, 迫切需要设计一种创新的电催化反应体系来加速偶联反应提高亚胺的产率.

本文在常温常压条件下采用富含硫空位的Co₉S₈纳米花催化剂(Co₉S₈-V_s), 在水相介质中通过硝基芳烃和芳基醛之间的电催化C-N偶联反应, 实现了亚胺的高选择性电合成. 电化学晶体石英微天平(EQCM)测试和第一性原理(DFT)计算结果表明, 引入带正电的硫空位可以有效地增强带负电的硝基苯和苯甲醛的吸附, 促进了电化学硝基苯还原反应(eNB-RR)的速率和转化率. 此外, 苯甲醛的吸附增强导致其在电极界面积聚, 从而加快了席夫碱缩合反应速率, 提高了亚胺生成的选择性. 最后, 生成的亚胺容易在催化剂界面解吸, 提供了额外的活性位点, 间接促进了eNB-RR的速率, 从而提高了硝基苯的转化率. 研究结果还表明, 该电催化合成亚胺化合物的方法对各种芳基醛和硝基芳烃的C-N偶联反应具有普遍的适用性. 在Co₉S₈-V_s阴极催化剂上考察了硝基苯与苯甲醛的克级电还原偶联制备亚胺产物的可行性, 在0 V_RHE条件下, 10 mmol硝基苯的转化率为98.4%, 亚胺产物选择性为90.1%. N-苄叉苯胺是制造生物活性化合物的重要组成部分, 因此我们也进行了亚胺产物的后期官能团化处理. 亚胺的Diels-Alder偶联反应突出了硝基苯与苯甲醛电还原偶联反应产物的适用性. β-内酰胺可以通过亚胺与三甲基硅烯醇酯进行Mannich-type加成和环化反应得到, 产物收率高达90%. 亚胺后期官能团化处理的产物二氢吡啶酮衍生物和β-内酰胺是生物活性化合物的主要核心支架, 证明了亚胺的广泛适用性.

综上所述, 本文提出了一种具有高效、环保的合成高附加值产物亚胺的电化学策略, 利用硫空位调节电极界面微环境从而实现电催化还原硝基芳烃和苯甲醛高效C-N偶联构建亚胺化合物, 为未来电催化合成亚胺提供了一条简便、环保的新途径.

关键词: 钴基电催化剂, 硫空位, 电催化, 电还原偶联

Abstract:

The electrocatalytic synthesis of imines through the reductive imination of nitroarenes with aldehydes is a facile, environmentally friendly, and valuable process. In this study, high selectivity electrosynthesis of imines was realized through the electrocatalytic C-N coupling reaction between nitroarenes and aryl aldehydes on Co₉S₈ nanoflowers with rich sulfur vacancies (Co₉S₈-V_s). Comparative experiments revealed that positively charged sulfur vacancies play a pivotal role in boosting catalytic selectivity towards imines. Electron-deficient sulfur vacancies intensified the adsorption of negatively charged Ph-NO₂, thereby enhancing the conversion rate of the electrochemical nitrobenzene-reduction reaction (eNB-RR). Simultaneously, sulfur vacancies augmented the adsorption capability of negatively charged Ph-CHO, enriching Ph-CHO species at the electrode interface and expediting the Schiff base condensation reaction rate. The experimental results show that the reaction conditions can satisfy the different nitroarenes and aryl aldehydes in the electrocatalytic aqueous-phase system under mild conditions to obtain the corresponding imine products in high selectivity. This study provides a facile and environmentally friendly pathway for future electrocatalytic synthesis of imine.

Key words: Co-based electrocatalyst, Sulfur-vacancies, Electrocatalysis, Electroreduction coupling

谢典科, 杨天仪, 马重阳, 董崇礼, 王双印, 邹雨芹. 硫空位促进硝基芳烃与芳基醛电化学还原偶联高选择性电合成亚胺[J]. 催化学报, 2024, 65: 206-216.

Dianke Xie, Tianyi Yang, Chongyang Ma, Chung-Li Dong, Shuangyin Wang, Yuqin Zou. Highly selective electrosynthesis of imines via electroreduction coupling of nitroarenes with aryl aldehydes on Co₉S₈ with positively charged sulfur vacancies[J]. Chinese Journal of Catalysis, 2024, 65: 206-216.

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图/表 8

Scheme 1. Schematic comparison of the thermodynamic and electrochemical strategy for imines production.

Fig. 1. Physical characterization of Co9S8 and Co9S8-Vs. (a) XRD patterns; high-resolution XPS spectra of Co 2p (b) and S 2p (c); (d) EPR spectra; (e) normalized Co K-edge XANES spectra; (f) corresponding FT-EXAFS spectra of Co9S8 and Co9S8-Vs.

Fig. 2. The electrochemical performance and activation characterization. (a) LSV curves of Co9S8 and Co9S8-Vs at a scan rate of 10 mV s?1 in the electrolyte with and without different substrates. (b) Selectivity and conversion over Co9S8 and Co9S8-Vs within 2 h at 0 VRHE. Potential-dependent selectivity of product and conversion of Ph-NO2 over Co9S8 (c) and Co9S8-Vs (d) within 2 h at +0.2 to ?0.4 VRHE. Coulomb-dependent evolution of each product over Co9S8 (e) and Co9S8-Vs (f).

Fig. 3. The adsorption behaviors of organic substrate on electrocatalytic. OCP curves of Co9S8 and Co9S8-Vs in the electrolyte when Ph-NO2 (a) and Ph-CHO (b) were injected. EQCM curves of Co9S8 and Co9S8-Vs when Ph-NO2 (c) and Ph-CHO (d) were injected. (e) Scheme of sulfur vacancies regulating the surface micro-environment of Co9S8-Vs catalyst.

Fig. 4. Unveiling the reaction pathway by in situ infrared spectroscopy. (a) In situ infrared spectroscopy of Co9S8-Vs electrode; (b) Detailed diagram of in situ infrared spectroscopy; (c) Schematic of the proposed reaction pathway (the numbering of the highlighted purple bonds in the schematic corresponds to the numbering in Fig. 4(b)).

Fig. 5. Quantum mechanics density functional theory calculations. (a) Computational energy profile of optimized intermediates on Co9S8 (440) and Co9S8-Vs (440); (b) Calculated Ph-NH2 and Ph-N=CH-Ph desorption energy; (c) Time-dependent conversion of Ph-NO2 over Co9S8 and Co9S8-Vs in an electrolyte containing Ph-NO2 only and both Ph-NO2 and Ph-CHO.

Scheme 2. Substrate scope of electroreduction coupling of nitroarenes with aryl aldehydes over the Co9S8-Vs cathode. Nitroarenes substrates (0.1 mmol), aryl aldehydes substrates (0.5 mmol), Ti-supported Co9S8-Vs (working area: 1 cm2), the electrolyte was a mixture of 1 mol L?1 KOH and ethanol with a volume ratio of 1:1 (10 mL), room temperature, 0 VRHE. The con. and sel. were determined by gas chromatography-mass spectrometry.

Scheme 3. The gram-scale reaction and Late-stage functionalization. (a) The gram-scale reaction of the electroreduction coupling of nitrobenzene with benzaldehyde over the Co9S8-Vs cathode. Late-stage functionalization: (b) Aza Diels-Alder reaction of the imine; (c) Mannich-type addition and cyclization via imine with trimethylsilyl enolates.

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硫空位促进硝基芳烃与芳基醛电化学还原偶联高选择性电合成亚胺

Highly selective electrosynthesis of imines via electroreduction coupling of nitroarenes with aryl aldehydes on Co₉S₈ with positively charged sulfur vacancies

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硫空位促进硝基芳烃与芳基醛电化学还原偶联高选择性电合成亚胺

Highly selective electrosynthesis of imines via electroreduction coupling of nitroarenes with aryl aldehydes on Co9S8 with positively charged sulfur vacancies

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Highly selective electrosynthesis of imines via electroreduction coupling of nitroarenes with aryl aldehydes on Co₉S₈ with positively charged sulfur vacancies