Citation: XU Kerui, ZHONG Zhiming, XU Huidong, WANG Xuan, ZHAO Min, WU Chuande. Highly Efficient Aerobic Oxidation of Arylalkanes with a Biomimetic Catalyst Platform[J]. Chinese Journal of Applied Chemistry, ;2017, 34(9): 1079-1085. doi: 10.11944/j.issn.1000-0518.2017.09.170191 shu

Highly Efficient Aerobic Oxidation of Arylalkanes with a Biomimetic Catalyst Platform

State Key Laboratory of Silicon Materials, Department of Chemistry, Zhejiang University, Hangzhou 310027, China

Corresponding author: WU Chuande, cdwu@zju.edu.cn

^‡

Received Date: 2 June 2017
Revised Date: 26 June 2017
Accepted Date: 27 June 2017

Fund Project: Supported by the National Natural Science Foundation of China(No.21373180, No.21525312), the Fundamental Research Funds for the Central Universities(No.2017XZZX001-03A, No.2017FZA3007)the Fundamental Research Funds for the Central Universities 2017XZZX001-03Athe Fundamental Research Funds for the Central Universities 2017FZA3007the National Natural Science Foundation of China 21373180the National Natural Science Foundation of China 21525312

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It is a challenge to oxidize inert hydrocarbons with molecular oxygen, which can be easily realized by enzymes under mild conditions. Inspired by the catalytic mechanism of enzymes, we used the composite material CuPW₁₁@HKUST-1, consisting of encapsulated Keggin-type polyoxometalate[CuPW₁₁O₃₉]^5-(abbreviated as CuPW₁₁) in the pore space of metal-organic framework HKUST-1, as a redox catalyst, and N-hydroxyphthalimide(NHPI) as a co-catalyst, for the biomimetic aerobic oxidation of arylalkanes under mild conditions. The biomimetic system exhibits enzyme-like features of high efficiency and high selectivity in the aerobic oxidation of arylalkanes by imitating the structural features, active sites and catalytic mechanism of enzymes, in which up to 99% yield and 17700 turnover number(TON) have been realized in the aerobic oxidation reaction. This work offers a feasible pathway for highly efficient aerobic oxidation of inert organic molecules under mild conditions.
- biomimetic catalysis,
- metal-organic frameworks,
- polyoxometalates,
- synergistic catalysis
1. [1]
  Hughes M D, Xu Y J, Jenkins P. Tunable Gold Catalysts for Selective Hydrocarbon Oxidation Under Mild Conditions[J]. Nature, 2005,437(7062):1132-1135. doi: 10.1038/nature04190
2. [2]
  Liese A, Seelbach K, Eds. Industrial Biotransformations[M]. Wandrey, C. Wiley-VCH, Weinhiem, 2006.
3. [3]
  Faber K. Biotransformations in Organic Chemistry[M]. Springer-Verlag, Berlin, 5^th ed, 2004.
4. [4]
  Kadish K M, Smith K M, Guilard R, Eds. The Porphyrin Handbook[M]. Academic Press, San Diego, 2000.
5. [5]
  Sheldon R A. Metalloporphyrins in Catalytic Oxidation[M]. Marcel Dekker, Basel, 1994.
6. [6]
  Wang S S, Yang G Y. Recent Advances in Polyoxometalate-Catalyzed Reactions[J]. Chem Rev, 2015,115(11):4893-4962. doi: 10.1021/cr500390v
7. [7]
  Ye J J, Wu C D. Immobilization of Polyoxometalates in Crystalline Solids for Highly Efficient Heterogeneous Catalysis[J]. Dalton Trans, 2016,45(25):10101-10112. doi: 10.1039/C6DT01378C
8. [8]
  Zhou H C, Long J R, Yaghi O M. Metal-Organic Frameworks Special Issue[J]. Chem Rev, 2012,112(2):673-1268. doi: 10.1021/cr300014x
9. [9]
  Zhou H C, Kitagawa S. Themed Issues on Metal-Organic Frameworks[J]. Chem Soc Rev, 2014,43(16):5415-6172. doi: 10.1039/C4CS90059F
10. [10]
  Zhao M, Ou S, Wu C D. Porous Metal-Organic Frameworks for Heterogeneous Biomimetic Catalysis[J]. Acc Chem Res, 2014,47(4):1199-1207. doi: 10.1021/ar400265x
11. [11]
  Zou C, Zhang Z, Xu X. A Multifunctional Organic-Inorganic Hybrid Structure Based on MnⅢ-Porphyrin and Polyoxometalate as a Highly Effective Dye Scavenger and Heterogenous Catalyst[J]. J Am Chem Soc, 2012,134(1):87-90. doi: 10.1021/ja209196t
12. [12]
  Yang X L, Xie M H, Zou C. Porous Metalloporphyrinic Frameworks Constructed from Metal 5, 10, 15, 20-Tetrakis(3, 5-biscarboxylphenyl)porphyrin for Highly Efficient and Selective Catalytic Oxidation of Alkylbenzenes[J]. J Am Chem Soc, 2012,134(25):10638-10645. doi: 10.1021/ja303728c
13. [13]
  Liu J, Chen L, Cui H. Applications of Metal Organic Frameworks in Heterogeneous Supramolecular Catalysis[J]. Chem Soc Rev, 2014,43(16):6011-6061. doi: 10.1039/C4CS00094C
14. [14]
  Ou S, Wu C D. Rational Construction of Metal-Organic Frameworks for Heterogeneous Catalysis[J]. Inorg Chem Front, 2014,1(10):721-734. doi: 10.1039/C4QI00111G
15. [15]
  Wu C D, Zhao M. Incorporation of Molecular Catalysts in Metal Organic Frameworks for Highly Efficient Heterogeneous Catalysis[J]. Adv Mater, 2017,29(14)1605446. doi: 10.1002/adma.v29.14
16. [16]
  Liu Y, Liu S, He D. Crystal Facets Make a Profound Difference in Polyoxometalate-Containing Metal-Organic Frameworks as Catalysts for Biodiesel Production[J]. J Am Chem Soc, 2015,137(39):12697-12703. doi: 10.1021/jacs.5b08273
17. [17]
  Sun C Y, Liu S X, Liang D D. Highly Stable Crystalline Catalysts Based on a Microporous Metal-Organic Framework and Polyoxometalates[J]. J Am Chem Soc, 2009,131(5):1883-1888. doi: 10.1021/ja807357r
18. [18]
  Zhao M, Ou S, Wu C D. Biomimetic Activation of Molecular Oxygen with a Combined Metalloporphyrinic Framework and Co-catalyst Platform[J]. ChemCatChem, 2017,9(3):1192-1196.
19. [19]
  Chui S S Y, Lo S M F, Charmant J P H. A Chemically Functionalizable Nanoporous Material[J]. Science, 1999,283(5405):1148-1150. doi: 10.1126/science.283.5405.1148
20. [20]
  Song J, Luo Z, Britt D K. A Multiunit Catalyst with Synergistic Stability and Reactivity:A Polyoxometalate Metal Organic Framework for Aerobic Decontamination[J]. J Am Chem Soc, 2011,133(42):16839-16846. doi: 10.1021/ja203695h
21. [21]
  Tourn C M, Tourn G F, Malik S A. Triheteropolyanions Containing Copper(Ⅱ), Manganese(Ⅱ), or Manganese(Ⅲ)[J]. J Inorg Nucl Chem, 1970,32(12):3875-3890. doi: 10.1016/0022-1902(70)80566-8
22. [22]
  Labinger J A, Bercaw J E. Understanding and Exploiting C-H Bond Activation[J]. Nature, 2002,417(6888):507-514. doi: 10.1038/417507a
23. [23]
  Bäckvall J E. Modern Oxidation Methods[M]. John Wiley, Weinheim, 2011.
24. [24]
  Recupero F C, Punta F. Free Radical Functionalization of Organic Compounds Catalyzed by N-Hydroxyphthalimide[J]. Chem Rev, 2007,107(9):3800-3842. doi: 10.1021/cr040170k
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