羰基化合物直接还原胺化合成伯胺催化剂研究进展

doi:10.16085/j.issn.1000-6613.2021-1551

摘要/Abstract

摘要：

胺类化合物是一类重要的化工原料和中间体，在农药、医药、染料、高分子聚合物等领域有着广泛的应用。通过羰基化合物（醛或酮类）的还原胺化来制备胺类化合物是当前的研究热点。研究表明，贵金属基和非贵金属基的多相和均相催化剂均能够高效催化醛或酮类的还原胺化反应。本文对近年来羰基化合物直接还原胺化（或一锅法）合成伯胺的研究现状进行了综述，包括还原胺化反应、催化剂、反应条件、底物适用范围和催化作用机制等，其中重点阐述了直接还原胺化催化剂的研究进展。文章指出：通常多相催化剂具有活性高以及可重复使用等优点，而均相催化剂的优势在于催化效率高，伯胺选择性高；另一方面，以Pd、Rh、Ru等为代表的贵金属催化剂催化性能优异，但价格昂贵，因此可采用Co、Ni等性能同样优异但价格相对低廉的非贵金属催化剂以降低成本。文中提出，催化效率高、反应条件温和、普适性高的羰基化合物还原胺化催化剂应成为未来重点研究方向。

关键词: 直接还原胺化, 羰基化合物, 伯胺, 均相催化, 多相催化, 催化剂

Abstract:

Amines, especially primary amines, have been extensively employed in pesticide, medicine, dye and high molecular polymer as raw materials or intermediates. Recently, direct reductive amination of carbonyl compounds (aldehydes or ketones) has been a research focus for synthesizing primary amines. Heterogeneous and homogeneous catalysts based on noble and non-noble metals have been proven to be efficient for direct reductive amination of carbonyl compounds. In this paper, we carefully review the state of art of direct reductive amination of carbonyl compounds (one-pot method) to synthesize primary amines, including reaction profile, recent progress in catalysts, reaction conditions, the substrate scope and catalytic mechanism, especially the catalysts. Generally, heterogeneous catalysts are highly active and could be reused, while homogeneous catalysts have the advantages of high efficiency and high primary amines selectivity. On the other hand, noble catalysts like Pd, Rh and Ru are more active and expensive, so non-noble metal based catalysts like Co and Ni catalysts could be alternative for the sake of economic. Thus, the catalysts for direct reductive amination to synthesize primary amines with high efficiency, mild reaction condition and high universality should be developed.

Key words: direct reductive amination, carbonyl compounds, primary amine, homogeneous catalysis, heterogeneous catalysis, catalysts

中图分类号:

O622.6

吴静航, 陈臣举, 梁杰, 张春雷. 羰基化合物直接还原胺化合成伯胺催化剂研究进展[J]. 化工进展, 2022, 41(6): 2981-2992.

WU Jinghang, CHEN Chenju, LIANG Jie, ZHANG Chunlei. Recent progress in the synthesis of primary amine via direct reductive amination of aldehydes and ketones[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 2981-2992.

图/表 12

参考文献 52

1	TALWAR D, SALGUERO N P, ROBERTSON C M, et al. Primary amines by transfer hydrogenative reductive amination of ketones by using cyclometalated Ir^Ⅲ catalysts[J]. Chemistry—A European Journal, 2014, 20(1): 245-252.
2	BÄHN S, IMM S, NEUBERT L, et al. The catalytic amination of alcohols[J]. ChemCatChem, 2011, 3(12): 1853-1864.
3	KOBAYASHI S, ISHITANI H. Catalytic enantioselective addition to imines[J]. Chemical Reviews, 1999, 99(5): 1069-1094.
4	MURUGESAN K, SENTHAMARAI T, CHANDRASHEKHAR V G, et al. Catalytic reductive aminations using molecular hydrogen for synthesis of different kinds of amines[J]. Chemical Society Reviews, 2020, 49(17): 6273-6328.
5	杨萍, 刘敏节, 张昊, 等. 硝基芳烃与醇还原胺化: 催化剂和催化机制[J]. 化学进展, 2020, 32(1): 72-83.
	YANG Ping, LIU Minjie, ZHANG Hao, et al. Reductive amination of nitroarenes and alcohols: catalyst and catalytic mechanism[J]. Progress in Chemistry, 2020, 32(1): 72-83.
6	GUNANATHAN C, MILSTEIN D. Selective synthesis of primary amines directly from alcohols and ammonia[J]. Angewandte Chemie International Edition, 2008, 47(45): 8661-8664.
7	潘嘉晟, 王耀锋, 马爽爽, 等. 脂肪伯胺的合成及工业化研究进展[J]. 过程工程学报, 2021, 21(8): 905-917.
	PAN Jiasheng, WANG Yaofeng, MA Shuangshuang, et al. Research progress on synthesis and industrialization of fatty primary amines[J]. The Chinese Journal of Process Engineering, 2021, 21(8): 905-917.
8	YANG L C, WANG Y N, ZHANG Y, et al. Acid-assisted Ru-catalyzed enantioselective amination of 1,2-diols through borrowing hydrogen[J]. ACS Catalysis, 2017, 7(1): 93-97.
9	NOWROUZI N, JONAGHANI M Z. Highly selective mono-N-benzylation and amidation of amines with alcohols or carboxylic acids using the Ph₂PCl/I₂/imidazole reagent system[J]. Canadian Journal of Chemistry, 2012, 90(6): 498-509.
10	MARICHEV K O, TAKACS J M. Ruthenium-catalyzed amination of secondary alcohols using borrowing hydrogen methodology[J]. ACS Catalysis, 2016, 6(4): 2205-2210.
11	滕燕燕. 纳米Pt催化剂上芳香硝基化合物选择加氢性能的研究[D]. 大连: 大连理工大学, 2019.
	TENG Yanyan. Study on selective hydrogenation performance of aromatic nitro compounds over nano-Pt catalysts[D]. Dalian: Dalian University of Technology, 2019.
12	SUN S T, DU M Y, ZHAO R X, et al. Zn(0)-catalysed mild and selective hydrogenation of nitroarenes[J]. Green Chemistry, 2020, 22(14): 4640-4644.
13	曾云凤. 磷化镍催化腈类化合物选择性生成伯胺的研究[D]. 昆明: 云南师范大学, 2017.
	ZENG Yunfeng. Selective hydrogenation of nitriles to primary amines catalyzed by Ni₂P[D]. Kunming: Yunnan Normal University, 2017.
14	SANAGAWA A, NAGASHIMA H. Hydrosilane reduction of nitriles to primary amines by cobalt-isocyanide catalysts[J]. Organic Letters, 2019, 21(1): 287-291.
15	陈晓, 花文廷. 酰胺还原反应研究进展[J]. 化学通报, 2001, 64(12): 749-754.
	CHEN Xiao, HUA Wenting. Recent developments on selective reduction of amides[J]. Chemistry Bulletin, 2001, 64(12): 749-754.
16	王建红, 李骞, 何丽华, 等. Gabriel合成胺反应的工艺改进[J]. 化学研究, 2010, 21(4): 48-51.
	WANG Jianhong, LI Qian, HE Lihua, et al. Modification of process for synthesizing polyamine via Gabriel reaction[J]. Chemical Research, 2010, 21(4): 48-51.
17	PAN X H, ZHAO D X, SHI Y, et al. Synthesis of S-3-hydroxyadamantylglycine ester by a Pd/C promoted mild leuckart-wallach reaction and an L-dibenzoyltartaric acid resolution[J]. Journal of Chemical Research, 2015, 39(2): 108-111.
18	KLINKENBERG J L, HARTWIG J F. Catalytic organometallic reactions of ammonia[J]. Angewandte Chemie International Edition, 2011, 50(1): 86-95.
19	LIN S K, MARCH J. March’s advanced organic chemistry: reactions, mechanisms, and structure, 5th edition[J]. Molecules, 2001, 6(12): 1064-1065.
20	高爽. 过渡金属催化酮直接不对称还原胺化合成伯胺及其衍生物[D]. 哈尔滨：哈尔滨工业大学, 2019.
	GAO Shuang. Transition metal-catalyzed direct asymmetric reductive amination of ketones for the synthesis of primary amines and their derivatives[D]. Harbin: Harbin Institute of Technology, 2019.
21	ABDEL-MAGID A F, CARSON K G, HARRIS B D, et al. Reductive amination of aldehydes and ketones with sodium triacetoxyborohydride. studies on direct and indirect reductive amination procedures1[J]. The Journal of Organic Chemistry, 1996, 61(11): 3849-3862.
22	IRRGANG T, KEMPE R. Transition-metal-catalyzed reductive amination employing hydrogen[J]. Chemical Reviews, 2020, 120(17): 9583-9674.
23	WINANS C F. Hydrogenation of aldehydes in the presence of ammonia[J]. Journal of the American Chemical Society, 1939, 61(12): 3566-3567.
24	HASKELBERG L. Aminative reduction of ketones[J]. Journal of the American Chemical Society, 1948, 70(8): 2811-2812.
25	王建强, 陈明明, 刘巍, 等. 固定床雷尼金属催化剂研究进展[J]. 化工进展, 2018, 37(11): 4280-4285.
	WANG Jianqiang, CHEN Mingming, LIU Wei, et al. Advance in fixed-bed Raney metal catalysts[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4280-4285.
26	CHATTERJEE M, ISHIZAKA T, KAWANAMI H. Reductive amination of furfural to furfurylamine using aqueous ammonia solution and molecular hydrogen: an environmentally friendly approach[J]. Green Chemistry, 2016, 18(2): 487-496.
27	熊曼, 黄磊, 刘晓云, 等. 铑催化的还原胺化合成一级胺[J]. 南京工业大学学报(自然科学版), 2014, 36(4): 13-17, 44.
	XIONG Man, HUANG Lei, LIU Xiaoyun, et al. Rhodium catalyzed reductive amination of aldehydes to primary amines with ammonium acetate[J]. Journal of Nanjing Tech University (Natural Science Edition), 2014, 36(4): 13-17, 44.
28	DONG B, GUO X C, ZHANG B, et al. Heterogeneous Ru-based catalysts for one-pot synthesis of primary amines from aldehydes and ammonia[J]. Catalysts, 2015, 5(4): 2258-2270.
29	KOMANOYA T, KINEMURA T, KITA Y, et al. Electronic effect of ruthenium nanoparticles on efficient reductive amination of carbonyl compounds[J]. Journal of the American Chemical Society, 2017, 139(33): 11493-11499.
30	GUO W J, TONG T, LIU X H, et al. Morphology-tuned activity of Ru/Nb₂O₅ catalysts for ketone reductive amination[J]. ChemCatChem, 2019, 11(16): 4130-4138.
31	DONG C L, WANG H T, DU H C, et al. Ru/HZSM-5 as an efficient and recyclable catalyst for reductive amination of furfural to furfurylamine[J]. Molecular Catalysis, 2020, 482: 110755.
32	LIANG G F, WANG A Q, LI L, et al. Production of primary amines by reductive amination of biomass-derived aldehydes/ketones[J]. Angewandte Chemie International Edition, 2017, 129(11): 3096-3100.
33	黄龙俊, 鲍佳浩, 郭璐瑶, 等. Ru/ZrO₂催化环己酮还原胺化制备环己胺工艺[J]. 化学反应工程与工艺, 2019, 35(3): 274-281.
	HUANG Longjun, BAO Jiahao, GUO Luyao, et al. Study on Ru/ZrO₂ catalyzed reductive amination of cyclohexanone to cyclohexylamine[J]. Chemical Reaction Engineering and Technology, 2019, 35(3): 274-281.
34	NAKAMURA Y, KON K, TOUCHY A S, et al. Selective synthesis of primary amines by reductive amination of ketones with ammonia over supported Pt catalysts[J]. ChemCatChem, 2015, 7(6): 921-924.
35	JV X, SUN S T, ZHANG Q, et al. Efficient and mild reductive amination of carbonyl compounds catalyzed by dual-function palladium nanoparticles[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(3): 1618-1626.
36	JAGADEESH R V, MURUGESAN K, ALSHAMMARI A S, et al. MOF-derived cobalt nanoparticles catalyze a general synthesis of amines[J]. Science, 2017, 358(6361): 326-332.
37	MURUGESAN K, CHANDRASHEKHAR V G, SENTHAMARAI T, et al. Reductive amination using cobalt-based nanoparticles for synthesis of amines[J]. Nature Protocols, 2020, 15(4): 1313-1337.
38	YUAN Z L, LIU B, ZHOU P, et al. Preparation of nitrogen-doped carbon supported cobalt catalysts and its application in the reductive amination[J]. Journal of Catalysis, 2019, 370: 347-356.
39	LIU J M, GUO W W, SUN H, et al. Reductive amination of carbonyl compounds with ammonia and hydrogenation of nitriles to primary amines with heterogeneous cobalt catalysts[J]. Chemical Research in Chinese Universities, 2019, 35(3): 457-462.
40	ZHANG Y M, YANG H M, CHI Q, et al. Nitrogen-doped carbon-supported nickel nanoparticles: a robust catalyst to bridge the hydrogenation of nitriles and the reductive amination of carbonyl compounds for the synthesis of primary amines[J]. ChemSusChem, 2019, 12(6): 1246-1255.
41	BÄUMLER C, BAUER C, KEMPE R. The synthesis of primary amines through reductive amination employing an iron catalyst[J]. ChemSusChem, 2020, 13(12): 3110-3114.
42	HAHN G, KUNNAS P, DE JONGE N, et al. General synthesis of primary amines via reductive amination employing a reusable nickel catalyst[J]. Nature Catalysis, 2019, 2(1): 71-77.
43	MURUGESAN K, BELLER M, JAGADEESH R V. Reusable nickel nanoparticles-catalyzed reductive amination for selective synthesis of primary amines[J]. Angewandte Chemie International Edition, 2019, 58(15): 5064-5068.
44	杜小宝. 芳香醛酮的绿色还原和三丙酮胺的还原胺化研究[D]. 天津: 天津大学, 2014.
	DU Xiaobao. Studies on the green reduction of aromatic aldehydes and ketones and the reductive amination of triacetoneamine[D]. Tianjin: Tianjin University, 2014.
45	GROSS T, SEAYAD A M, AHMAD M, et al. Synthesis of primary amines: first homogeneously catalyzed reductive amination with ammonia[J]. Organic Letters, 2002, 4(12): 2055-2058.
46	GALLARDO-DONAIRE J, ERNST M, TRAPP O, et al. Direct synthesis of primary amines via ruthenium-catalysed amination of ketones with ammonia and hydrogen[J]. Advanced Synthesis & Catalysis, 2016, 358(3): 358-363.
47	GHOSH T, ERNST M, HASHMI A S K, et al. Ruthenium catalyzed direct asymmetric reductive amination of simple aliphatic ketones using ammonium iodide and hydrogen[J]. European Journal of Organic Chemistry, 2020, 2020(30): 4796-4800.
48	SENTHAMARAI T, MURUGESAN K, SCHNEIDEWIND J, et al. Simple ruthenium-catalyzed reductive amination enables the synthesis of a broad range of primary amines[J]. Nature Communications, 2018, 9: 4123.
49	PAN J S, ZHANG R, MA S S, et al. Easily synthesized Ru catalyst efficiently converts carbonyl compounds and ammonia into primary amines[J]. ChemistrySelect, 2020, 5(35): 10933-10938.
50	TANAKA K, MIKI T, MURATA K, et al. Reductive amination of ketonic compounds catalyzed by Cp*Ir(Ⅲ) complexes bearing a picolinamidato ligand[J]. The Journal of Organic Chemistry, 2019, 84(17): 10962-10977.
51	MURUGESAN K, WEI Z H, CHANDRASHEKHAR V G, et al. Homogeneous cobalt-catalyzed reductive amination for synthesis of functionalized primary amines[J]. Nature Communications, 2019, 10: 5443.
52	MURUGESAN K, WEI Z H, CHANDRASHEKHAR V G, et al. General and selective synthesis of primary amines using Ni-based homogeneous catalysts[J]. Chemical Science, 2020, 11(17): 4332-4339.

催化剂	反应条件	反应底物	反应结果
Rh/Al₂O₃^［26］	80℃，氨水，2MPa H₂，2h	糠醛	X_糠醛=100%，S_糠胺=91.5%
Rh/CeO₂^［27］	50℃，0.1MPa H₂，14h	苯甲醛	X_苯甲醛=100%，S_苄胺=88%
Ru/γ-Al₂O₃^［28］	80℃，0.4MPa NH₃，3MPa H₂，2h	庚醛	X_庚醛=100%，S_庚胺=94%
Ru/Nb₂O₅^［29］	90℃，0.1MPa NH₃，4MPa H₂，4h	糠醛	X_糠醛=100%，S_糠胺=99%
Ru/HZSM-5^［31］	80℃，NH₃（7mol/L MeOH 溶液），3MPa H₂，15min	糠醛	X_糠醛=100%，S_糠胺=76%
Ru/ZrO₂^［32］	85℃，氨水，2MPa H₂，12h	乙醇醛	X_乙醇醛=100%，S_乙醇胺=93%
Pt-MoO _x /TiO₂^［34］	100℃，0.4MPa NH₃，0.2MPa H₂，20h	2-金刚烷酮	X_{2-金刚烷酮}=100%，S_{2-金刚烷胺}=93%
Pd/NPs^［35］	室温，NH₃，0.1MPa H₂，3h	苯甲醛	X_苯甲醛=100%，S_苄胺=98%

催化剂	反应条件	反应底物	反应结果
Rh/Al₂O₃^［26］	80℃，氨水，2MPa H₂，2h	糠醛	X_糠醛=100%，S_糠胺=91.5%
Rh/CeO₂^［27］	50℃，0.1MPa H₂，14h	苯甲醛	X_苯甲醛=100%，S_苄胺=88%
Ru/γ-Al₂O₃^［28］	80℃，0.4MPa NH₃，3MPa H₂，2h	庚醛	X_庚醛=100%，S_庚胺=94%
Ru/Nb₂O₅^［29］	90℃，0.1MPa NH₃，4MPa H₂，4h	糠醛	X_糠醛=100%，S_糠胺=99%
Ru/HZSM-5^［31］	80℃，NH₃（7mol/L MeOH 溶液），3MPa H₂，15min	糠醛	X_糠醛=100%，S_糠胺=76%
Ru/ZrO₂^［32］	85℃，氨水，2MPa H₂，12h	乙醇醛	X_乙醇醛=100%，S_乙醇胺=93%
Pt-MoO _x /TiO₂^［34］	100℃，0.4MPa NH₃，0.2MPa H₂，20h	2-金刚烷酮	X_{2-金刚烷酮}=100%，S_{2-金刚烷胺}=93%
Pd/NPs^［35］	室温，NH₃，0.1MPa H₂，3h	苯甲醛	X_苯甲醛=100%，S_苄胺=98%

催化剂	反应条件	反应底物	反应结果
Co-DABCO-TPA@C-800^［36］	120℃，0.5MPa NH₃，4MPa H₂，15h	3,4-二甲氧基苯甲醛	Y_{3,4-二甲氧基苄胺}=88%
Co/GS@C^［37］	120℃，0.5MPa NH₃，4MPa H₂，15h	苯甲醛	Y_卞胺=88%
Co@NC-800^［38］	130℃，氨水，1MPa H₂，12h	苯甲醛	Y_卞胺=96.9%
Co@NC^［39］	110℃，氨水，2MPa H₂，5h	对甲氧基苯甲醛	Y_{对甲氧基卞胺}=94.5%
Ni/MC^［40］	80℃，氨水，0.1MPa H₂，2h	苯甲醛	Y_苄胺=99.1%
Fe/(N)SiC^［41］	140℃，氨水，6.5MPa H₂，20h	苯乙酮	Y_1-苯乙胺=99%
Ni/γ-Al₂O₃^［42］	80℃，氨水，0.1MPa H₂，20h	苯甲醛	Y_苄胺=99%
Ni-TA@SiO₂-800^［43］	120℃，0.5MPa NH₃，2MPa H₂，15h	邻溴苯甲醛	Y_邻溴卞胺=96%

催化剂	反应条件	反应底物	反应结果
Co-DABCO-TPA@C-800^［36］	120℃，0.5MPa NH₃，4MPa H₂，15h	3,4-二甲氧基苯甲醛	Y_{3,4-二甲氧基苄胺}=88%
Co/GS@C^［37］	120℃，0.5MPa NH₃，4MPa H₂，15h	苯甲醛	Y_卞胺=88%
Co@NC-800^［38］	130℃，氨水，1MPa H₂，12h	苯甲醛	Y_卞胺=96.9%
Co@NC^［39］	110℃，氨水，2MPa H₂，5h	对甲氧基苯甲醛	Y_{对甲氧基卞胺}=94.5%
Ni/MC^［40］	80℃，氨水，0.1MPa H₂，2h	苯甲醛	Y_苄胺=99.1%
Fe/(N)SiC^［41］	140℃，氨水，6.5MPa H₂，20h	苯乙酮	Y_1-苯乙胺=99%
Ni/γ-Al₂O₃^［42］	80℃，氨水，0.1MPa H₂，20h	苯甲醛	Y_苄胺=99%
Ni-TA@SiO₂-800^［43］	120℃，0.5MPa NH₃，2MPa H₂，15h	邻溴苯甲醛	Y_邻溴卞胺=96%

催化剂	反应条件	反应底物	反应结果
[Rh(COD)Cl]₂/TPPTS^[45]	135℃，氨水，6.5MPa H₂，2h	苯甲醛	Y_苄胺=86%
[Ru(CO)ClH(PPh₃)₃]^[46]	120℃，0.9MPa NH₃，4MPa H₂，16h	苯乙酮	Y_α-苯乙胺=95%
[Ru(PPh₃)₃H(CO)Cl]^[47]	80℃，NH₄I，3MPa H₂，24h	甲基酮环己酯	Y₍_S_{)-(+)-1-环己基乙胺}=78%
RuCl₂(PPh₃)₃^[48]	120℃，0.5~0.7MPa NH₃，4MPa H₂，24h	苯甲醛	Y_卞胺=95%
Ru-1^［49］	130℃，0.5MPa NH₃，5MPa H₂，12h	苯甲醛	Y_苄胺=94%
Cp*Ir^［50］	80℃，甲酸铵，4h	苯乙酮	Y_1-苯乙胺=97%