Use of CuO encapsulated in mesoporous silica SBA-15 as a recycled catalyst for allylic C–H bond oxidation of cyclic olefins at room temperature†

Saadi Samadi*ab, Akram Ashouria and Mehdi Ghambarianc aLaboratory of Asymmetric Synthesis, Department of Chemistry, Faculty of Science, University of Kurdistan, Zip Code 66177-15175, Sanandaj, Iran. E-mail: s.samadi@uok.ac.ir bResearch Centre of Nanotechnology, University of Kurdistan, P.O. Box 416, Sanandaj, Iran cGas Conversion Department, Faculty of Petrochemicals, Iran Polymer and Petrochemical Institute, P.O. Box 14975-112, Tehran, Iran

First published on 31st March 2017

1. Introduction

The direct functionalization of sp3 C-H bonds is one of the most important reactions in organic synthesis.1-4 Oxidation reaction of these bonds at the allylic position of cycloolefins (Kharash-Sosnovsky reaction) can be used as one of the most straightforward synthetic routes for the preparation of highly functionalized olefins such as allylic esters and allylic alcohols that are important intermediates in the synthesis of leukotriene B4 (ref. 5) chrysanthemic acid,6 brevetoxin7 and amyrin.8 The nature of the metal salt, perester oxidant, and reaction conditions including solvent and temperature are affected this reaction remarkably.9-17

Allylic C-H bond oxidation have been studied by homogeneous catalysts such as selenium,18-24 selenium dioxide,18-21,23 diselenides24 and pentafluorobenzeneselenic acid18-24 with different metals such as Hg(II),25-30 Pd(II),31-37 Pb(IV),25 Cr(VI),25,38,39 Co(III),40,41 Co(II),42-44 Mn(III),41,45,46 Ce(IV),41 Fe(II),47 Rh(II),48 Rh(I),49,50 Cu5-13 and a variety of ligands. However, copper-catalysis - due to its low cost - is the most popular in this field, although their large industrial scale usage is limited.

On the other side, supported nanometals are one of the most important categories of heterogeneous catalysts with broad applications in the industry. Some materials, such as SBA-15, MCM-41 and zeolite were applied for the preparation of metal nanoparticles.

Among them, SBA-15 has some advantages such as hexagonally arrayed channels and narrow pore size distribution so that it has attracted great attention.51-53 Immobilization of metal NPs within a silica scaffold prevents agglomeration and surface fouling, and aids in NP recovery and recycling.54-57

In our previous work, we reported the effect of some additives such activated silica gel, mesoporous MCM-41, SBA-15 silica, nanocrystalline MgO, CuO and TiO2 on this reaction and SBA-15 was shown better results than others.58-61 The strong effect of these additives encouraged us to prepare and characterize CuO encapsulated in mesoporous silica SBA-15 with various Cu loadings in the range of 1-12 wt% by an impregnation method in three routes, which was applied in allylic C-H bond oxidation of cyclic olefins.1-13

2. Experimental

2.1. General remarks

All reagents and starting materials were purchased from Aldrich, Merck, Fluka and Sigma. Cycloolefins were distilled from calcium hydride before use. All solvents for the reactions were also dried and distilled immediately before use. Melting points were measured on an Electrothermal 9100 apparatus and are uncorrected. Fourier transform infrared (FT-IR) spectrum was recorded on a Bruker Vector 22 spectrometer using pressed KBr pellets. X-ray diffraction patterns were obtained on a Simens D500 diffractometer with Cu Kα radiation. The SEM image and EDX patterns were taken using VEGATESCAN. The surface area was calculated by the BET method in Quantachrome Instruments.

2.2. The preparation of heterogeneous catalysts

The preparation of Cu-B-N-SBA-15 was drown in Scheme 1.

2.3. Allylic C-H bond oxidation of cyclic olefins

Allylic oxidation of cycloolefins was drown in Scheme 2.

3. Results and discussions

3.1. Characterization of heterogeneous catalyst

The catalyst was characterized by XRD, EDX, BET, SEM, AAS and FT-IR.

3.2. Catalytic effects in allylic C-H bond oxidation of cyclic olefins

4. Conclusions

In conclusion, CuO encapsulated in mesoporous silica SBA-15 as monometallic catalysts has been synthesized through the reaction of SBA-15 or aminopropyl modified SBA-15 with Cu(NO3)2 under different conditions. The catalytic potential of these heterogeneous catalysts was applied for the copper-catalyzed allylic oxidation of cycloolefins via sp3 C-H bond activation. Allylic esters were prepared in good yields, reasonably short period of time and high selectivity in acetonitrile in the presence of 40 mg of Cu-B-N-SBA-15 with 9 wt% loading of copper. For cyclohexene in comparison with other cycloolefins, the best result in term of yield (99%) and rate of reaction (25 h) was obtained.

Mild conditions of this reaction in combination with recyclability of the catalyst, make the presented work a desire approach to produce functionalized olefins in compared to the most of reports.

Acknowledgements

We are grateful to the University of Kurdistan Research Councils for the support of this work.

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Footnote

† Electronic supplementary information (ESI) available: Supplementary data (included IR, 1H and 13C spectra of compounds 1-5 and the procedure of synthesis 1, IR, SEM, EDX, X-ray scattering and elemental mapping for prepared catalysts and the typical procedure for the synthesis of SBA-15, NH2-SBA-15). See DOI: 10.1039/c7ra02995kThis journal is © The Royal Society of Chemistry 2017

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