镍纳米颗粒催化氢化和氘化合成一般胺

doi:10.1016/S1872-2067(25)64658-4

催化学报 ›› 2025, Vol. 72: 392-401.DOI: 10.1016/S1872-2067(25)64658-4

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镍纳米颗粒催化氢化和氘化合成一般胺

王晓飞^,¹, 李延^,¹, 王梦云, 高一鸣, 马壮, 雷爱文^*(), 李武^*()

武汉大学化学与分子科学学院, 高等研究院, 湖北武汉 430072

收稿日期:2024-11-20 接受日期:2025-01-25 出版日期:2025-05-18 发布日期:2025-05-20
通讯作者: *电子信箱: aiwenlei@whu.edu.cn (雷爱文),wu.li@whu.edu.cn (李武)
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(212200007);国家自然科学基金(22031008);国家重点研发计划(2022 YFA1505100);国家重点研发计划(2021 YFA1500100);武汉市科学基金(2020010601012192)

Nickel nanoparticles catalyzed hydrogenation and deuteration for a general amine synthesis

Xiaofei Wang^,¹, Yan Li^,¹, Mengyun Wang, Yiming Gao, Zhuang Ma, Aiwen Lei^*(), Wu Li^*()

The Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China

Received:2024-11-20 Accepted:2025-01-25 Online:2025-05-18 Published:2025-05-20
Contact: *E-mail: aiwenlei@whu.edu.cn (A. Lei), wu.li@whu.edu.cn (W. Li).
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(212200007);National Natural Science Foundation of China(22031008);National Key R&D Program of China(2022 YFA1505100);National Key R&D Program of China(2021 YFA1500100);Science Foundation of Wuhan(2020010601012192)

摘要/Abstract

摘要：

胺是各种化学领域中的常见基序, 广泛应用于农用化学品和医药领域. 开发用于合成胺的地球丰产金属基异相催化剂仍然是化学研究和工业应用/制造方面的一个重要目标. 在此, 我们开发了一种富含路易斯酸位点的高效、高选择性氮掺杂镍催化剂, 并将其用于腈和胺的氢化偶联, 合成了一系列功能化、结构多样化的仲胺和叔胺. 此外, 在更温和的条件下还实现了腈的催化氢化和氘化, 合成了一系列伯胺和具有高氚代率的胺.

在所有已知的合成伯胺和取代胺的方法中, 以氢气为还原剂的催化氢化是一种成本效益高、原子经济的方法. 非均相催化剂具有可重复使用性、更好的反应选择性、更容易的产物/催化剂分离和低廉的成本. 本文采用氮掺杂催化剂改性策略, 通过控制氮配体、纳米颗粒的尺寸、分布以及载体的表面组成来调节负载金属纳米催化剂的活性, 成功实现了廉价镍基纳米催化剂催化的腈和胺的氢化偶联反应. 透射电镜、X射线光电子能谱、粉末X射线衍射、氢气程序升温还原以及氨气程序升温脱附等结果表明, 镍纳米催化剂的活性来源是氮掺杂和氧空位的协同作用. 研究表明, 多种不同取代的芳基腈以及烷基腈均可与胺发生加氢偶联反应, 并且胺的种类包括苯胺类、伯胺和仲胺, 高效、高选择性地构建了一系列官能团丰富结构多样的胺类化合物. 该方法还可在较为温和的条件(5 bar H₂/D₂, 80 °C)下实现腈的催化氢化和氘化, 合成了一类官能团兼容性良好的伯胺化合物和氘代伯胺化合物. 此外, 催化剂能够循环10次仍保持较高的催化活性以及成功实现了在3 g以及10 g规模的药物合成, 显示了该方法在工业上具有非常高的潜在应用价值. 最后本文阐述了可能的反应机理: 先经过腈催化半氢化到亚胺中间体, 再与偶联组分胺发生缩合反应脱去一分子氨, 得到新的亚胺中间体, 然后继续被催化氢化得到目标产物.

综上所述, 本文开发了一种富含路易斯酸位点的氮掺杂镍催化剂, 在温和条件下实现腈与胺的高选择性氢化偶联反应和腈的催化氢化反应, 合成了一系列高产率的伯胺、仲胺和叔胺, 且具有良好的官能团耐受性以及使用D₂制备了一类高氘代率的胺化合物, 并且可用于合成普通药物和氘代药物, 代表了一种新的腈化合物转化方法, 为制备具有不同结构的胺和α-氘代胺提供了另一条途径.

关键词: 氮掺杂纳米镍催化, 氢化偶联反应, 催化氢化和氘化, 胺和氘代胺

Abstract:

Amines represent fundamental motifs in various chemical contexts and are widely used in agrochemicals and pharmaceuticals. The development of earth-abundant metal-based heterogeneous catalysts for the synthesis amines remains an important goal in terms of chemical research and industrial application/manufacture. Herein, we developed an efficient and highly selective nitrogen-doped nickel catalyst enriched with Lewis acid sites, which has been applied for to the hydrogenative coupling of nitriles and amines with molecular hydrogen for the synthesis of a train of functionalised and structurally diverse secondary and tertiary amines. Furthermore, catalytic hydrogenation and deuteration of nitriles were achieved under milder conditions, yielding a series of primary amines and deuterated amines with high deuterium incorporation.

Key words: Nitrogen-doped nano-nickel catalysis, Hydrogenative coupling reaction, Catalytic hydrogenation and deuteration, Amines and deuterated amines

王晓飞, 李延, 王梦云, 高一鸣, 马壮, 雷爱文, 李武. 镍纳米颗粒催化氢化和氘化合成一般胺[J]. 催化学报, 2025, 72: 392-401.

Xiaofei Wang, Yan Li, Mengyun Wang, Yiming Gao, Zhuang Ma, Aiwen Lei, Wu Li. Nickel nanoparticles catalyzed hydrogenation and deuteration for a general amine synthesis[J]. Chinese Journal of Catalysis, 2025, 72: 392-401.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64658-4

https://www.cjcatal.com/CN/Y2025/V72/I5/392

图/表 8

Fig. 1. Catalytic reductive cross coupling of nitriles with primary or secondary amines or ammonia and formation of different products.

Table 1 Condition optimization.

Entry	Catalyst	1 Yield %
1	Ni-Phen@C-800	n.d.
2	Ni-Phen@Al₂O₃-800	28
3	Ni-Phen@SiO₂-800	n.d.
4	Ni-Phen@TiO₂-800	n.d.
5	Ni-Phen@ZrO₂-800	45
6	Ni-Phen@CeO₂-800	trace
7	Ni-Aniline@ZrO₂-800	trace
8	Ni-OPD@ZrO₂-800	72(64)
9	Ni-Melamine@ZrO₂-800	trace
10	Ni-OPD@ZrO₂-600	trace
11	Ni-OPD@ZrO₂-1000	23
12	Ni@ZrO₂-800	35
13	OPD@ZrO₂-800	n.d.

Fig. 2. Characterizations of Ni-OPD@ZrO2. TEM (a) and high-magnification TEM (b) images of Ni-OPD@ZrO2, inset with corresponding size distribution and selected-area electron diffraction (SAED) patterns. The corresponding energy dispersive spectrum (EDS) (c), STEM (d) and mapping (d1-d6) images with various element of Ni-OPD@ZrO2. HR-XPS spectra of Ni 2p (e), N 1s (f) and O 1s (g) between ZrO2, Ni@ZrO2 and Ni-OPD@ZrO2. UPS spectra in the cutoff (Ecutoff) of ZrO2 (h), Ni-OPD (i), and Ni-OPD@ZrO2 (j).

Scheme 1. Synthesis of secondary and tertiary amines by Ni-catalyzed hydrogenative cross coupling of nitriles and amines. Reaction conditions: 0.5 mmol nitrile, 0.75 mmol amine, 100 mg Ni-OPD@ZrO2 (10 mol%), 1 mL H2O, 1 mL 1.4-dioxane, 30 bar H2, 120 °C, 20 h. Isolated yields were given. a 0.3 mL aq. N,N-dimethylamine; b 50 bar H2, 140 °C; *scale up for 18: The reactions were performed at 2 g Ni-OPD@ZrO2, 40 mL H2O, 40 mL 1,4-dioxane, 50 bar H2, 140 °C, 48 h, isolated yield.

Scheme 2. Ni-catalyzed catalytic hydrogenative and deuteration of nitriles. Reaction conditions: 0.5 mmol nitrile, 100 mg Ni-OPD@ZrO2 (10 mol%), 1 mL aq. ammonia, 1 mL 1,4-dioxane, 5 bar H2, 80 °C, 20 h. Isolated yields were given. a GC yield; b 10 bar H2, 80 °C; c The reactions were performed at 0.5 mmol nitrile, 100 mg Ni-OPD@ZrO2 (10 mol%), 1 mmol (NH4)2CO3, 1 mL D2O, 1 mL 1.4-dioxane, 5 bar D2 and 5 bar N2, 120 °C, 20 h. Isolated yields were given. Products were isolated as free amines and converted to their hydrochloride salts for NMR and high-resolution mass spectrometry (HRMS) analysis.

Fig. 3. Catalyst recycling experiments.

Fig. 4. Synthetic applications.

Fig. 5. Proposed mechanism.

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镍纳米颗粒催化氢化和氘化合成一般胺

Nickel nanoparticles catalyzed hydrogenation and deuteration for a general amine synthesis

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