Citation: Mengyang LI, Hao XU, Zhonghao NIU, Chunhua GONG, Weihui ZHONG, Jingli XIE. Highly effective catalytic synthesis of β-amino alcohols by using viologen-polyoxometalate hybrid materials[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(7): 1294-1300. doi: 10.11862/CJIC.20250080 shu

Highly effective catalytic synthesis of β-amino alcohols by using viologen-polyoxometalate hybrid materials

Mengyang LI ^{1, 2} ,
Hao XU ² ,
Zhonghao NIU ² ,
Chunhua GONG ³ ,
Weihui ZHONG ^1,, ,
Jingli XIE ^2,,

1.
College of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 341014, China
2.
College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, Zhejiang 314001, China
3.
School of Advanced Materials and Engineering, Jiaxing Nanhu University, Jiaxing, Zhejiang 314001, China

Corresponding author: Weihui ZHONG, weihuizhong@zjut.edu.cn Jingli XIE, jlxie@mail.zjxu.edu.cn
Received Date: 11 March 2025
Revised Date: 6 May 2025

Figures(7)

The crystalline material (MV)₂[HPW^Ⅴ₂W^Ⅵ₁₀O₄₀]·2H₂O achieved from 1, 1′-dimethyl 4, 4′-bipyridine (methyl viologen, MV) dichloride and Keggin-type polyoxometalate unit, was used as a highly efficient catalyst for the synthesis of β-amino alcohols under organic solvent-free and room temperature conditions. Experimental results showed that the catalyst could efficiently accelerate the synthesis of β-amino alcohols while maintaining its stability. It could be reused six times and there was no significant decrease in its catalytic activity, indicating its certain recyclability. Compared with traditional synthetic methods, this system demonstrated its advantages in organic solvent-free, mild experimental conditions, simple procedures, and environmentally friendly conditions.
- viologen,
- polyoxometalate,
- catalytic application,
- β-amino alcohols
1. [1]
  YIN X J, GONG W Z, ZENG Y J, QIU H L, LIU L, HOLLMANN F, CHEN B H. Substrate-specific evolution of amine dehydrogenases for accessing structurally diverse enantiopure (R)-β-amino alcohols[J]. ACS Catal., 2024, 14(2): 837-845 doi: 10.1021/acscatal.3c04995
2. [2]
  HU H, WANG Z B. Cr-catalyzed asymmetric cross aza-pinacol couplings for β-amino alcohol synthesis[J]. J. Am. Chem. Soc., 2023, 145(38): 20775-20781 doi: 10.1021/jacs.3c08493
3. [3]
  LIU S Z, WANG S C, WANG P J, HUANG Z L, WANG T, LEI A W. 1, 2-Amino oxygenation of alkenes with hydrogen evolution reaction[J]. Nat. Commun., 2022, 13: 4430 doi: 10.1038/s41467-022-32084-8
4. [4]
  COREY E J, ZHANG F Y. re- and si-face-selective nitroaldol reactions catalyzed by a rigid chiral quaternary ammonium salt: A highly stereoselective synthesis of the HIV protease inhibitor amprenavir (Vertex 478)[J]. Angew. Chem.‒Int. Edit., 1999, 38: 1931-1934 doi: 10.1002/(SICI)1521-3773(19990712)38:13/14<1931::AID-ANIE1931>3.0.CO;2-4
5. [5]
  O′BRIEN P. Sharpless asymmetric aminohydroxylation: Scope, limitations, and use in synthesis[J]. Angew. Chem.‒Int. Edit., 1999, 38: 326-329 doi: 10.1002/(SICI)1521-3773(19990201)38:3<326::AID-ANIE326>3.0.CO;2-T
6. [6]
  AGER D J, PRAKASH I, SCHAAD D R. 1, 2-Amino alcohols and their heterocyclic derivatives as chiral auxiliaries in asymmetric synthesis[J]. Chem. Rev., 1996, 96(2): 835-876 doi: 10.1021/cr9500038
7. [7]
  HERAV M M, LASHAKI T B, FATTAHI B, ZADSIRJAN V. Application of asymmetric sharpless aminohydroxylation in total synthesis of natural products and some synthetic complex bio-active molecules[J]. RSC Adv., 2018, 8: 6635
8. [8]
  ZHOU Z J, TAN, Y Q, SHEN X, SERGEI I, ERIC M. Catalytic enantioselective synthesis of β-amino alcohols by nitrene insertion[J]. Sci. China: Chem., 2021, 64(3): 452-458 doi: 10.1007/s11426-020-9906-x
9. [9]
  NAKAFUKU K M; ZHANG Z X, WAPPES E A, STATEMAN L M, CHEN AN D, NAGIB D A. Enantioselective radical C-H amination for the synthesis of β-amino alcohols[J]. Nat. Chem., 2020, 12(8): 697-704 doi: 10.1038/s41557-020-0482-8
10. [10]
  REDDY U V S, CHENNAPURAM M, SEKI C, KWON E, OKUYAMA Y, NAKANO H. Catalytic efficiency of primary β-amino alcohols and their derivatives in organocatalysis[J]. Eur. J. Org. Chem., 2016, 2016: 4124-4143 doi: 10.1002/ejoc.201600164
11. [11]
  SHI C Y, REN C, ZHANG E, JIN H L, YU X C, WANG S. Synthesis of β-amino alcohols using the tandem reduction and ring-opening reaction of nitroarenes and epoxides[J]. Tetrahedron, 2016, 72(27/28): 3839-3843
12. [12]
  ZHANG J Q, GAO H, GAO L L, CHEN M Y, HUANG S P, ZHANG J D. Biocatalytic asymmetric ring-opening of meso-epoxides to enantiopure cyclic trans-β-amino alcohols involving a key amine transaminase[J]. Green Chem., 2024, 26: 6160 doi: 10.1039/D4GC00827H
13. [13]
  REISER O. The sharpless asymmetric aminohydroxylation of olefins[J]. Angew. Chem.‒Int. Edit., 1996, 35: 1308-1309 doi: 10.1002/anie.199613081
14. [14]
  AZIZI N, SAIDI M R. Highly chemoselective addition of amines to epoxides in water[J]. Org. Lett., 2005, 7: 3649-3651 doi: 10.1021/ol051220q
15. [15]
  AZOULAY S, MANABE K, KOBAYASHI S. Catalytic asymmetric ring opening of meso-epoxides with aromatic amines in water[J]. Org. Lett., 2005, 7: 4593-4595 doi: 10.1021/ol051546z
16. [16]
  LIU B X, XIE P F, ZHAO J, WANG J J, WANG M M, JIANG Y Q, CHANG J B, LI X W. Rhodium-catalyzed enantioselective synthesis of β-amino alcohols via desymmetrization of gem-dimethyl groups[J]. Angew. Chem.‒Int. Edit., 2021, 60: 8396-8400 doi: 10.1002/anie.202014080
17. [17]
  CHARLES L K, BRUCE R. Base-induced rearrangement of epoxides. Ⅳ. reaction of cyclohexene oxide with various lithium alkylamides[J]. J. Org. Chem., 1972, 37(13): 2060-2063 doi: 10.1021/jo00978a002
18. [18]
  SEKAR B S, MAO J, LUKITO B R, WANG Z, LI Z. Bioproduction of enantiopure (R)- and (S)-2-phenylglycinols from styrenes and renewable feedstocks[J]. Adv. Synth. Catal., 2021, 363: 1892-1903 doi: 10.1002/adsc.202001322
19. [19]
  ZHANG J D, YANG X X, DONG R, GAO L L, LI J, LI X, HUANG S P, ZHANG C F, CHANG H H. Cascade biocatalysis for regio- and stereoselective aminohydroxylation of styrenyl olefins to enantiopure arylglycinols[J]. ACS Sustain. Chem. Eng., 2020, 8: 18277-18285 doi: 10.1021/acssuschemeng.0c06819
20. [20]
  THIERRY O, GUILLAUME L C. An efficient method for the ring opening of epoxides with aromatic amines catalyzed by bismuth trichloride[J]. Tetrahedron Lett., 2002, 43(44): 781-7893
21. [21]
  GOVINDARAJAN S, KARI V, BABU V. Synthesis of β-amino alcohols by regioselective ring opening of arylepoxides with anilines catalyzed by cobaltous chloride[J]. Tetrahedron Lett., 2004, 45(44): 8353-8256
22. [22]
  CURINI M, EPIFANO F, MARCOTULLIO M, ROSATI O. Zirconium sulfophenyl phosphonate as a heterogeneous catalyst in the preparation of β-amino alcohols from epoxides[J]. Eur. J. Org. Chem., 2001, 21: 4149-4152
23. [23]
  HERAVI M M, BAGHERNEJAD B, OSKOOIE H A. A new strategy for the aminolysis of epoxides with amines under solvent free conditions using Fe-MCM-41 as a novel and efficient catalyst[J]. Catal. Lett., 2009, 130: 547-550 doi: 10.1007/s10562-009-9898-x
24. [24]
  XUE W M, KUNG M C, KOZLOV A I, POPP K E, KUNG H H. Catalytic aminolysis of epoxide by alumina prepared from amine-protected Al precursor[J]. Catal. Today, 2003, 85(2): 219-224
25. [25]
  CHAKRABORTI A K, KONDASKAR A, RUDRAWAR S. Scope and limitations of montmorillonite K 10 catalysed opening of epoxide rings by amines[J]. Tetrahedron, 2004, 60(41): 9085-9091 doi: 10.1016/j.tet.2004.07.077
26. [26]
  KURESHY R I, SINGH S, KHAN N H, ABDI S H R, SURESH E, JASRA R V. Efficient method for ring opening of epoxides with amines by NaY zeolite under solvent-free conditions[J]. J. Mol. Catal. A‒Chem., 2007, 264(1): 162-169
27. [27]
  LI B N, CHEN MX, HU Q Y, ZHU J Y, YANG X, LI Z X, HU C L, LI Y Y, NI P, DING Y. Facilely tunable dodecahedral polyoxometalate framework loaded with mono- or bimetallic sites for efficient photocatalytic CO₂ reduction[J]. Appl. Catal. B‒Environ., 2024, 346: 123733 doi: 10.1016/j.apcatb.2024.123733
28. [28]
  FU S H, KHAN S U, YANG R R, PANG H J, AU C M, MA H Y, WANG X M, YANG G X, SUN W L, YU W Y. High-performance heterometallic photocatalysts afforded by polyoxometalate synthons for efficient H₂ production[J]. J. Colloid Interface Sci., 2024, 666: 496-504 doi: 10.1016/j.jcis.2024.04.057
29. [29]
  FENG Y, FU F, ZENG L, ZHAO M, XIN X, LIANG J, ZHOU M, FANG X, LV H, YANG G Y. Atomically precise silver clusters stabilized by lacunary polyoxometalates with photocatalytic CO₂ reduction activity[J]. Angew. Chem.‒Int. Edit., 2024, 63: e202317341 doi: 10.1002/anie.202317341
30. [30]
  LIANG Y, ZHANG Z, SU X, FENG X, XING S, LIU W, HUANG R, LIU Y. Coordination defect-induced frustrated Lewis pairs in polyoxo-metalate-based metal-organic frameworks for efficient catalytic hydrogenation[J]. Angew. Chem.‒Int. Edit., 2023, 62: e202309030 doi: 10.1002/anie.202309030
31. [31]
  MATEOS P S, RUSCITTI C B, CASELLA M L, MATKOVIC S R, BRIAND L E. Phosphotungstic wells-dawson heteropolyacid as potential catalyst in the transesterification of waste cooking oil[J]. Catalysts, 2023, 13: 1253 doi: 10.3390/catal13091253
32. [32]
  SI C, LIU X L, ZHANG T, XU J B, LI J, FU J Y, HAN Q X. Constructing a photocatalyst for selective oxidation of benzyl alcohol to benzaldehyde by photo-Fenton-like catalysis[J]. Inorg. Chem., 2023, 62(10): 4210-4219 doi: 10.1021/acs.inorgchem.2c04318
33. [33]
  XU B J, XU Q, WANG Q Z, LIU Z, ZHAO R K, LI D P, MA P T, WANG J P, NIU J Y. A copper-containing polyoxometalate-based metal-organic framework as an efficient catalyst for selective catalytic oxidation of alkylbenzenes[J]. Inorg. Chem., 2021, 60(7): 4792-4799 doi: 10.1021/acs.inorgchem.0c03741
34. [34]
  ZHANG Q Y, YANG T Y, LIU X F, YUE C Y, AO L F, DENG T L, ZHANG Y T. Heteropoly acid-encapsulated metal-organic framework as a stable and highly efficient nanocatalyst for esterification reaction[J]. RSC Adv., 2019, 9: 16357-16365 doi: 10.1039/C9RA03209F
35. [35]
  LIU Y, LIU Q Y, SUN K H, ZHAO S F, KIM Y D, YANG Y P, LIU Z Y, PENG Z K. Identification of the encapsulation effect of heteropolyacid in the Si-Al framework toward benzene alkylation[J]. ACS Catal., 2022, 12(8): 4765-4776 doi: 10.1021/acscatal.1c05895
36. [36]
  AZIZI N, SAIDI M R. Highly efficient ring opening reactions of epoxides with deactivated aromatic amines catalyzed by heteropoly acids in water[J]. Tetrahedron Lett., 2007, 63(4): 888-891 doi: 10.1016/j.tet.2006.11.045
37. [37]
  LIU H R, XU H, ZHU D R, ZHANG J Y, GONG C H, XIE J L. Syntheses, structures, photochromic and photocatalytic properties of two viologen-polyoxometalate hybrid materials[J]. Chinese J. Inorg. Chem., 2024, 40(7): 1368-1376 doi: 10.11862/CJIC.20240066
38. [38]
  PARKER R E, ISAACS N S. Mechanisms of epoxide reactions[J]. Chem. Rev., 1959, 59(4): 727-799
39. [39]
  SAIKIA L, SATYARTHI J K, SRINIVAS D, RATNASAMY P. Activation and reactivity of epoxides on solid acid catalysts[J]. J. Catal., 2007, 252(2): 148-160 doi: 10.1016/j.jcat.2007.10.002
1. [1]
  Huirong LIU , Hao XU , Dunru ZHU , Junyong ZHANG , Chunhua GONG , Jingli XIE . Syntheses, structures, photochromic and photocatalytic properties of two viologen-polyoxometalate hybrid materials. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1368-1376. doi: 10.11862/CJIC.20240066
2. [2]
  Xiaonan LI , Hui HAN , Yihan ZHANG , Jing XIONG , Tingting GUO , Juanzhi YAN . A viologen‐based Cd(Ⅱ) coordination polymer: Self‐assembly, thermochromism, and electrochemical property. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1439-1444. doi: 10.11862/CJIC.20240376
3. [3]
  Runjie Li , Hang Liu , Xisheng Wang , Wanqun Zhang , Wanqun Hu , Kaiping Yang , Qiang Zhou , Si Liu , Pingping Zhu , Wei Shao . 氨基酸的衍生及手性气相色谱分离创新实验. University Chemistry, 2025, 40(6): 286-295. doi: 10.12461/PKU.DXHX202407059
4. [4]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
5. [5]
  Ruiying WANG , Hui WANG , Fenglan CHAI , Zhinan ZUO , Benlai WU . Three-dimensional homochiral Eu(Ⅲ) coordination polymer and its amino acid configuration recognition. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 877-884. doi: 10.11862/CJIC.20250052
6. [6]
  Xingyuan Lu , Yutao Yao , Junjing Gu , Peifeng Su . Energy Decomposition Analysis and Its Application in the Many-Body Effect of Water Clusters. University Chemistry, 2025, 40(3): 100-107. doi: 10.12461/PKU.DXHX202405074
7. [7]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
8. [8]
  Hong CAI , Jiewen WU , Jingyun LI , Lixian CHEN , Siqi XIAO , Dan LI . Synthesis of a zinc-cobalt bimetallic adenine metal-organic framework for the recognition of sulfur-containing amino acids. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 114-122. doi: 10.11862/CJIC.20240382
9. [9]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
10. [10]
  Liang TANG , Jingfei NI , Kang XIAO , Xiangmei LIU . Synthesis and X-ray imaging application of lanthanide-organic complex-based scintillators. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1892-1902. doi: 10.11862/CJIC.20240139
11. [11]
  Zhaoxuan ZHU , Lixin WANG , Xiaoning TANG , Long LI , Yan SHI , Jiaojing SHAO . Application of poly(vinyl alcohol) conductive hydrogel electrolytes in zinc ion batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 893-902. doi: 10.11862/CJIC.20240368
12. [12]
  Yifeng TAN , Ping CAO , Kai MA , Jingtong LI , Yuheng WANG . Synthesis of pentaerythritol tetra(2-ethylthylhexoate) catalyzed by h-MoO₃/SiO₂. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2155-2162. doi: 10.11862/CJIC.20240147
13. [13]
  Yuanyuan Ping , Wangqing Kong . 光催化碳氢键官能团化合成1-苯基-1,2-乙二醇. University Chemistry, 2025, 40(6): 238-247. doi: 10.12461/PKU.DXHX202408092
14. [14]
  Pengcheng Yan , Peng Wang , Jing Huang , Zhao Mo , Li Xu , Yun Chen , Yu Zhang , Zhichong Qi , Hui Xu , Henan Li . Engineering Multiple Optimization Strategy on Bismuth Oxyhalide Photoactive Materials for Efficient Photoelectrochemical Applications. Acta Physico-Chimica Sinica, 2025, 41(2): 100014-. doi: 10.3866/PKU.WHXB202309047
15. [15]
  Ran Yu , Chen Hu , Ruili Guo , Ruonan Liu , Lixing Xia , Cenyu Yang , Jianglan Shui . 杂多酸H₃PW₁₂O₄₀高效催化MgH₂储氢. Acta Physico-Chimica Sinica, 2025, 41(1): 2308032-. doi: 10.3866/PKU.WHXB202308032
16. [16]
  Lirui Shen , Kun Liu , Ying Yang , Dongwan Li , Wengui Chang . Synthesis and Application of Decanedioic Acid-N-Hydroxysuccinimide Ester: Exploration of Teaching Reform in Comprehensive Applied Chemistry Experiment. University Chemistry, 2024, 39(8): 212-220. doi: 10.3866/PKU.DXHX202312035
17. [17]
  Guoqiang Chen , Zixuan Zheng , Wei Zhong , Guohong Wang , Xinhe Wu . 熔融中间体运输导向合成富氨基g-C₃N₄纳米片用于高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406021-. doi: 10.3866/PKU.WHXB202406021
18. [18]
  Linjie ZHU , Xufeng LIU . Synthesis, characterization and electrocatalytic hydrogen evolution of two di-iron complexes containing a phosphine ligand with a pendant amine. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 939-947. doi: 10.11862/CJIC.20240416
19. [19]
  Shitao Fu , Jianming Zhang , Cancan Cao , Zhihui Wang , Chaoran Qin , Jian Zhang , Hui Xiong . Study on the Stability of Purple Cabbage Pigment. University Chemistry, 2024, 39(4): 367-372. doi: 10.3866/PKU.DXHX202401059
20. [20]
  Jingzhao Cheng , Shiyu Gao , Bei Cheng , Kai Yang , Wang Wang , Shaowen Cao . 4-氨基-1H-咪唑-5-甲腈修饰供体-受体型氮化碳光催化剂的构建及其高效光催化产氢研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406026-. doi: 10.3866/PKU.WHXB202406026

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(13)
HTML views(6)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142