Citation: Wang Yifan, Fan Yimei, Jian Jun, Pan Yumin, Zhao Liang, Jing Xueping, Zhou Shengjia, Chen Xiaohong, Du Quan, Wang Ling, Wu Xiaoju, Fu Xiangkai. Synthesis of Chiral Salen Mn (Ⅲ) Complex Immobilized on Phenoxy-modified AlPS-PVPA as Catalysts for Epoxidation of Olefins[J]. Acta Chimica Sinica, ;2017, 75(7): 715-722. doi: 10.6023/A17010002 shu

Synthesis of Chiral Salen Mn (Ⅲ) Complex Immobilized on Phenoxy-modified AlPS-PVPA as Catalysts for Epoxidation of Olefins

Wang Yifan ^a ,
Fan Yimei ^b ,
Jian Jun ^a ,
Pan Yumin ^a ,
Zhao Liang ^a ,
Jing Xueping ^a ,
Zhou Shengjia ^c ,
Chen Xiaohong ^a,*,, ,
Du Quan ^a ,
Wang Ling ^a ,
Wu Xiaoju ^d ,
Fu Xiangkai ^d

a.
School of Science, Xihua University, Chengdu 610039
b.
School of Construction and Management Engineering, Xihua University, Chengdu 610039
c.
School of Electrical and Electronic Information, Xihua University, Chengdu 610039
d.
College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715

Corresponding author: Chen Xiaohong, shengxiaohongb@163.com
Received Date: 2 January 2017

Fund Project: the Innovation Fund of Postgraduate, Xihua University ycjj2017101the key research fund of Sichuan Provincial Department of Education 14ZA0113

Figures(14)

Chiral epoxides are versatile intermediates that can be readily converted into a wide variety of enantiomerically pure compounds by means of region-and stereo-selective ring opening reactions.The asymmetric epoxidation of unfunctionalized olefins is an important approach for synthesizing optically active epoxides, and thus is widely used in the synthesis of fine chemicals, such as pharmaceuticals, agrochemicals and perfumes.Chiral salen Mn (Ⅲ) complexes have demonstrated activities and selectivities for the enantioselective epoxidation of unfunctionalized olefins under homogeneous conditions.Compared with the homogeneous asymmetric catalysts, the heterogeneous ones have the advantages of easy catalyst/product separation and simple catalyst recycling.And more and more interests have been focused on the studies of heterogenization of chiral complexes.New types of supported catalysts are obtained by anchoring chiral salen Mn (Ⅲ) complex on a series of phenoxy-modified aluminium poly (styrene-phenylvinylphosphonate)-phosphate (AlPS-PVPA) in the text.All the prepared catalysts are characterized by FT-IR, UV-vis, XPS, SEM, TG and elemental analysis.The catalytic capabilities are investigated with m-CPBA as an oxidant and with indene and α-methylstyrene as substrates for asymmetric epoxidation of unfunctionalized olefins.The supported catalysts indicate superior catalytic activities in the asymmetric epoxidation of α-methylstyrene and indene with m-CPBA as oxidative system, compared with the corresponding homogeneous catalyst (ee, > 97% vs.54% and > 99% vs.65%).The steric properties of the linkages really play vital impacts on the configuration of the transition state for the asymmetric reactions.Contrary to most of the literatures reported, the results show that the heterogeneous catalysts 3a~3d exhibit excellent catalytic activities, and their conversions and ee values increase remarkably in the absence of N-methylmorpholine N-oxide (NMO) under the same catalytic conditions.The structures of the immobilized cat-alysts similar to the N-oxide ligand act as axial ligands leading to the unusual phenomenon.Simultaneously, additives are generally regarded as axial ligands on the transition metal catalyst, which make for activating the catalyst either toward oxidation or toward reactivity with the olefin.Thus, there is a steric hindrance when the N-oxide ligand is added and the optimal geometric configuration of the reactive intermediate salen Mn (V)=O was altered.It is steric hindrance that makes olefins approaching salen Mn (V)=O difficult and lower ee values are obtained.Furthermore, these catalysts are easily separated and are relatively stable and reused nine times without significant loss of activities.
- aluminium poly (styrene-phenylvinylphosphonate)-phosphate,
- phenoxy-modified,
- salen Mn (Ⅲ),
- unfunctionalized olefins,
- asymmetric epoxidation
1. [1]
  McGarrigle, E. M.; Gilheany, D. G. Chem. Rev. 2005, 105(5), 1563. doi: 10.1021/cr0306945
2. [2]
  Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112(7), 2801. doi: 10.1021/ja00163a052
3. [3]
  Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. doi: 10.1021/ja00080a070
4. [4]
  Xia, Q. H.; Ge, H. Q.; Ye, C. P.; Liu, Z. M.; Su, K. X. Chem. Rev. 2005, 105, 1603. doi: 10.1021/cr0406458
5. [5]
  Li, C.; Zhang, H. D.; Jiang, D. M.; Yang, Q. H. Chem. Commun. 2007, 547.
6. [6]
  Zou, X. C.; Shi, K. Y.; Li, J.; Wang, Y.; Deng, C. F.; Ren, Y. R.; Tan, J.; Fu, X. K. Chin. J. Org. Chem. 2016, 36, 1765.
7. [7]
  Zou, X. C.; Fu, X. K.; Luo, Y. F. Acta Chim. Sinica 2011, 69, 431.
8. [8]
  Bai, R. F.; Fu, X. K.; Bao, H. B.; Ren, W. S. Catal. Commun. 2008, 9, 1588. doi: 10.1016/j.catcom.2008.01.014
9. [9]
  Ren, W. S.; Fu, X. K. J. Mol. Catal. A:Chem. 2009, 312, 40. doi: 10.1016/j.molcata.2009.07.002
10. [10]
  Luo, Y. F.; Fu, X. K.; Zou, X. C.; Wang, C. Y.; Hu, X. Y.; Jia, Z. Y.; Zhang, H. Z. J. Inorg. Organomet. Polym. 2011, 21(2), 276. doi: 10.1007/s10904-010-9447-5
11. [11]
  Tu, X. B.; Fu, X. K.; Hu, X. Y.; Li, Y. D. Inorg. Chem. Commun. 2010, 13, 404. doi: 10.1016/j.inoche.2009.12.034
12. [12]
  Gong, B. W.; Fu, X. K.; Chen, J. X.; Li, Y. D.; Zou, X. C.; Tu, X. B.; Ding, P. P.; Ma, L. P. J. Catal. 2009, 262, 9. doi: 10.1016/j.jcat.2008.11.027
13. [13]
  Wang, C. W.; Fu, X. K.; Huang, J. Acta Chim. Sinica 2011, 69, 1681.
14. [14]
  Huang, J.; Fu, X. K.; Wang, G.; Li, C.; Hu, X. Y. Dalton Trans. 2011, 40, 3631. doi: 10.1039/c0dt01553a
15. [15]
  Hu, X. Y.; Fu, X. K.; Xu, J. W.; Wang, C. W. J. Organomet. Chem. 2011, 696, 2797. doi: 10.1016/j.jorganchem.2011.04.027
16. [16]
  Thomas, J.; Raja, M. R.; Sankar, G.; Bell, R. G. Nature 1999, 398(6724), 227. doi: 10.1038/18417
17. [17]
  Thomas, J. M.; Raja, R.; Sankar, G.; Bell, R. G. Acc. Chem. Res. 2001, 34(3), 191. doi: 10.1021/ar970020e
18. [18]
  Rao, C. N. R.; Natarajan, S. A.; Choudhury, S.; Neeraj, A. A. Acc. Chem. Res. 2001, 34(1), 80. doi: 10.1021/ar000135+
19. [19]
  Chong, K. C. W.; Sivaguru, J.; Shichi, T.; Yoshimi, Y.; Ramamurthy, V.; Scheffer, J. R. J. Am. Chem. Soc. 2002, 124(12), 2858. doi: 10.1021/ja016989m
20. [20]
  Joy, A.; Uppili, S.; Netherton, M. R.; Scheffer, J.; Ramamurthy, R. V. J. Am. Chem. Soc. 2000, 122(4), 728. doi: 10.1021/ja993746+
21. [21]
  Cowley, A. R.; Jones, R. H.; Teat, S. J.; Chippindale, A. M. Mi-croporous Mesoporous Mater. 2002, 51(1), 51. doi: 10.1016/S1387-1811(01)00474-7
22. [22]
  Zhao, Z. H. Chin. J. Syn. Chem. 2006, 14(1), 103.
23. [23]
  Huang, Q. W.; Zhang, S. Y. J. Mol. Catal. 2003, 17(6), 417.
24. [24]
  Zou, X. C.; Fu, X. K.; Li, Y. D.; Tu, X. B.; Fu, S. D.; Luo, Y. F.; Wu, X. J. Adv. Synth. Catal. 2010, 352, 163. doi: 10.1002/adsc.v352:1
25. [25]
  Silva, A. R.; Figueiredo, J. L.; Freire, C.; Castro, B. D. Microporous Mesoporous Mater. 2004, 68, 83. doi: 10.1016/j.micromeso.2003.12.002
26. [26]
  Duan, F. Z.; Li, J. Y.; Sun, W.; Chen, P.; Yu, J. H.; Xu, R. R. Sci. Chin. Chem. 2011, 41(1), 24.
27. [27]
  Wu, X. J.; Fu, X. K.; Huang, J.; Jia, Z. Y. Chin. J. Inorg. Chem. 2012, 28(11), 2341.
28. [28]
  Zhang, H. D.; Zhang, Y. M.; Li, C. Tetrahedron 2006, 62, 6640. doi: 10.1016/j.tet.2006.01.117
29. [29]
  Zhang, H. D.; Xiang, S.; Xiao, J. L.; Li, C. J. Mol. Catal. A:Chem. 2005, 238, 175. doi: 10.1016/j.molcata.2005.05.024
1. [1]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
2. [2]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
3. [3]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
4. [4]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
5. [5]
  Yongqing Kuang , Jie Liu , Jianjun Feng , Wen Yang , Shuanglian Cai , Ling Shi . Experimental Design for the Two-Step Synthesis of Paracetamol from 4-Hydroxyacetophenone. University Chemistry, 2024, 39(8): 331-337. doi: 10.12461/PKU.DXHX202403012
6. [6]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
7. [7]
  Shengbiao Zheng , Liang Li , Nini Zhang , Ruimin Bao , Ruizhang Hu , Jing Tang . Metal-Organic Framework-Derived Materials Modified Electrode for Electrochemical Sensing of Tert-Butylhydroquinone: A Recommended Comprehensive Chemistry Experiment for Translating Research Results. University Chemistry, 2024, 39(7): 345-353. doi: 10.3866/PKU.DXHX202310096
8. [8]
  Hongling Yuan , Jialin Xie , Jiawei Wang , Jixiang Zhao , Jiayan Liu , Qing Feng , Wei Qi , Min Liu . Cyclic Olefin Copolymer (COC): The Agile Vanguard in the Realm of Materials. University Chemistry, 2024, 39(7): 294-298. doi: 10.12461/PKU.DXHX202311041
9. [9]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
10. [10]
  Yingxian Wang , Tianye Su , Limiao Shen , Jinping Gao , Qinghe Wu . Introduction of Chinese Lacquer from the Perspective of Chemistry: Popularizing Chemistry in Lacquer and Inherit Lacquer Art. University Chemistry, 2024, 39(5): 371-379. doi: 10.3866/PKU.DXHX202312015
11. [11]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083
12. [12]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
13. [13]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
14. [14]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, 2024, 39(10): 408-415. doi: 10.12461/PKU.DXHX202403024
15. [15]
  Juan Yuan , Bin Zhang , Jinping Wu , Mengfan Wang . Design of a Comprehensive Experiment on Preparation and Characterization of Cu₂(Salen)₂ Nanomaterials with Two Distinct Morphologies. University Chemistry, 2024, 39(10): 420-425. doi: 10.3866/PKU.DXHX202402014
16. [16]
  Qiuyu Xiang , Chunhua Qu , Guang Xu , Yafei Yang , Yue Xia . A Journey beyond “Alum”. University Chemistry, 2024, 39(11): 189-195. doi: 10.12461/PKU.DXHX202404094
17. [17]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
18. [18]
  Tao Wen , Tao Zhang , Changguo Sun , Jinyu Liu . Preparation of Dess-Martin Reagent and Its Application in Oxidizing Cyclohexanol. University Chemistry, 2024, 39(5): 20-26. doi: 10.3866/PKU.DXHX202309055
19. [19]
  Lihui Jiang , Wanrong Dong , Hua Yang , Yongqing Xia , Hongjian Peng , Jun Yuan , Xiaoqian Hu , Zihan Zeng , Yingping Zou , Yiming Luo . Study on Extraction of p-Hydroxyacetophenone. University Chemistry, 2024, 39(11): 259-268. doi: 10.12461/PKU.DXHX202402056
20. [20]
  Hong Zheng , Xin Peng , Chunwang Yi . The Tale of Caprolactam Cyclic Oligomers: The Ever-changing Life of “Princess Cyclo”. University Chemistry, 2024, 39(9): 40-47. doi: 10.12461/PKU.DXHX202403058

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(1371)
HTML views(196)

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