Nickel nanoparticles catalyzed hydrogenation and deuteration for a general amine synthesis

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64658-4

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

Figures/Tables 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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