Magnetic nano-graphene oxide-supported molybdenum (Fe3O4/GO-Mo) as a green, efficient, and recyclable catalyst for synthesis of β-hydroxy hydroperoxides

Article abstract of DOI:10.1007/s00706-017-2092-8

Abstract: Magnetic nano-graphene oxide-supported molybdenum was readily prepared and identified as an efficient and recyclable catalyst for ring opening of various epoxides with ethereal hydrogen peroxide. The reaction proceeded under mild conditions to g

Full text of DOI:10.1007/s00706-017-2092-8

Monatsh Chem
https://doi.org/10.1007/s00706-017-2092-8
ORIGINAL PAPER
Magnetic nano-graphene oxide-supported molybdenum (Fe3O4/
GO-Mo) as a green, efficient, and recyclable catalyst for synthesis
of b-hydroxy hydroperoxides
Yu-Heng Liu1,2
Hai-Chuan Hu3 Zi-Chuan Ma1,3 Yan-Fei Dong3
•
•
•
•
Can Wang3 Yun-Meng Pang1
•
Received: 11 August 2017 / Accepted: 7 November 2017
Ó Springer-Verlag GmbH Austria, part of Springer Nature 2018
Abstract Magnetic
nano-graphene
oxide-supported
Keywords Epoxides Á Hydrogen peroxide Á
molybdenum was readily prepared and identified as an
efficient and recyclable catalyst for ring opening of various
epoxides with ethereal hydrogen peroxide. The reaction
proceeded under mild conditions to give b-hydroxy
hydroperoxides in excellent yields at room temperature.
The catalyst could be easily separated and recycled by
applying a permanent magnet.
b-Hydroxyhydroperoxides Á Magnetic nano-graphene oxide
Introduction
The development of novel, non-toxic, low-cost, eco-
friendly, recyclable, and high-efficient catalytic system has
been received a great deal of research attention in organic
synthesis for environmental and economic reasons. To
approach these goals, graphene oxide (GO) has been
widely explored to replace conventional catalysts or used
as supporting material for improving the performance of
catalysts due to its large specific surface area, unique lay-
ered structure, high mechanical strength, excellent
physicochemical stability, and high flexibility [1–5].
However, the tedious and expensive separation and
recovery of powdered nano-graphene is an obstacle ham-
pering for its industry-scale applications. Magnetic
separation is a simple, economical, and green approach,
which makes the removing and recycling of catalyst much
easier than filtration and centrifugation [6–10]. Thus, the
magnetic nano-graphene oxide (MNGO) catalysts may not
only effectively bridge the gap between homogeneous and
heterogeneous catalysis due to their good dispersion
properties, high catalytic activity, and selectivity, but also
efficaciously address the issues of separation, recovery, and
recycling of catalysts [11–13].
Graphical abstract
H2O2
Ethereal
O
OOH
R1
R1
R2
OH
R2
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s00706-017-2092-8) contains supple-
mentary material, which is available to authorized users.
& Yu-Heng Liu
liu2795478@163.com
& Zi-Chuan Ma
mazc@vip.163.com
b-Hydroxyhydroperoxides (HHPs) are important and
versatile intermediates in organic synthesis [14, 15]; par-
ticularly, they can be used as synthetic precursors for the
preparation of 1,2,4-trioxanes [16]. They also display
antimalarial activity [17], antitumor [18, 19], antitubercu-
losis [20, 21], and fasciocidal activity [22]. It has been
found that the construction of the peroxy bond in the
1
College of Life Science, Hebei Normal University,
Shijiazhuang 050024, China
2
College of Pharmaceutical Sciences, Hebei Medical
University, Shijiazhuang 050017, China
3
College of Chemistry and Material Science, Hebei Normal
University, Shijiazhuang 050024, China
123

Y.-H. Liu et al.
endoperoxides plays a key role in resistance to disease.
Thus, the introduction of peroxy bond in organic synthesis
has long been one of the most challenging research targets
[23–26]. Up to now, there have been two general approa-
ches to afford peroxy bond in the literatures. The first is the
addition reaction of singlet oxygen with allylic alcohols
[27–30]. This approach was associated with some disad-
vantages, such as restricted to an allylic specific alcohol
skeleton, unsatisfactory yields, toxic reagents, and high-
pressure oxygen. The second is the ring-opening reaction
of oxiranes via H2O2 for preparation of substituted HHPs
[31, 32], which can also avoid the use of the oxygen gas
tank. Thus, this approach becomes an important means for
preparing HHPs, which was originally catalyzed by strong
acids such as HClO4 [33] or CF3CO2H [34]. Recently,
some improved methods have been developed in the lit-
erature by employing MoO2(acac)2 [35], phosphomolybdic
acid (PMA) [36], SbCl3/SiO2 [37], tin(IV) chloride [38], or
magnetic nanoparticles (CoFe2O4)-supported phospho-
molybdate [39] as a catalyst. However, some of the
methods still have more or less drawbacks, such as using
unrecyclable catalysts, long reaction times, or dissatisfied
yield. Therefore, the design of a recyclable catalytic system
that promotes efficient ring opening of epoxides with H2O2
is still strongly desirable and of significant value.
Recently, we have discovered that magnetic GO
nanoparticles are excellent catalysts for the synthesis
of 3,6-di(pyridin-3-yl)-1H-pyrazolo[3,4-b]pyridine-5-car-
bonitriles [40] and spiro-oxindole-dihydropyridines [41].
As a continuation of our research on developing efficient
and environmental benign synthetic methodologies
[42–50], we report here a new type of MNGO-supported
molybdena (Fe3O4/GO-Mo) as an highly efficient, inex-
pensive, and recyclable catalyst for the synthesis of HHPs
(Scheme 1).
Results and discussion
Catalytic activity of Fe3O4/GO-Mo
Initially, the ring opening of 2-phenyloxirane (1 mmol) in
ethereal H2O2 (5 mmol) was used as the model reaction to
evaluate the activity of the prepared catalyst and the results
are presented in Table 1. It can be found that the catalyst
plays a vital role in the success of the reaction in terms of
both the rate and yields. Only traces of product were
obtained, even after 500 min, in the absence of catalyst
(Table 1, entry 1). Various nano-materials such as CoFe2-
O4, Fe3O4/GO-Cu, Fe3O4/GO-Co, Fe3O4/GO-Sn, and
Scheme 1
Table 1 Synthesis of 2-hydroperoxy-3-methoxy-1-phenylpropan-1-ol in various conditions
Entry
Catalyst
Catalyst loading/mol%
Time/min
Yielda/%
1
None
–
500
60
50
50
50
15
15
30
60
50
50
50
60
300
50
15
Trace
41
2
Fe3O4/GO-Cu
Fe3O4/GO-Co
Fe3O4/GO-Sn
Fe3O4/GO-Zn
Fe3O4/GO-Mo
Fe3O4/GO-Mo
Fe3O4/GO-Mo
CoFe2O4
20
20
20
20
20
10
5
3
38
4
47
5
27
6
94
7
96
8
85
9
20
20
20
20
20
20
20
20
24
10
11
12
13
14
15
16c
Phosphomolybdic acid
Ammonium phosphomolybdate
Molybdenyl acetylacetonate
Fe3O4
80
71
81
19
GO
Trace
21
Fe3O4/GO
Fe3O4/GO-Mo
94
Reaction conditions: phenyloxirane (1 mmol), 5 cm3 ethereal H2O2 (5 mmol), room temperature
aIsolated yields
bThe reaction was carried out in 10.0 mmol scale
123

Magnetic nano-graphene oxide-supported molybdenum (Fe3O4/GO-Mo) as a green, efficient…
Fe3O4/GO-Zn were investigated to promote this model
reaction, and 2-hydroperoxy-2-phenylethanol (2a) was
generated in lower yields (Table 1, entries 2–5). Further
study found that the reaction occurred smoothly in the
presence of Fe3O4/GO-Mo (20 mol% Mo), and the
expected product 2a was obtained in 94% yield (Table 1,
entry 6). Next, the quantity of the catalyst was investigated
in this reaction, and it was found that the use of just
10 mol% was sufficient to produce an excellent yield of the
product (Table 1, entry 7). For comparison, pure phos-
phomolybdic acid, ammonium phosphomolybdate, and
molybdenyl acetylacetonate were also tested as the
homogeneous catalysts. It was observed that the reaction
rate dropped and afforded the product in 80, 71 and 81%
yields, respectively, in 50 min (Table 1, entries 10–12).
Furthermore, Fe3O4, GO, and Fe3O4/GO were also exam-
ined to identify their catalytic activity, but received rarely
desired product. Based on the above results, the Fe3O4/GO-
Mo is the most effective catalyst for leading to the syn-
thesis of 2-hydroperoxy-2-phenylethanol in higher yield.
Again, the reaction was successfully performed at large
scale (10 mmol) without significant loss of yield (entry 16).
With the optimal reaction conditions in hand, the scope
and generality of the method were explored. As shown in
Table 2, the diverse epoxides with various sterically,
electronically, and functionally groups were easily and
efficiently converted to the corresponding hydroperoxy
alcohols in high yields. All reactions were completed in
15–20 min with good regioselectivity, being determined by
1H NMR and also by comparison with known samples. The
results of epoxides ring opening demonstrated that the
structure of epoxides exerts a significant effect on the
reaction. In the case of aryl epoxides, b-hydroperoxy
alcohols were obtained in a regioselective manner with
preferential attack at the more substituted carbon, since the
benzyl position of the epoxides is more positive and thus
more prone to attack by H2O2, even if the epoxides with a
space-hindered group would not affect on the yield of
provided 2-hydroperoxy-1,2-diphenylethanol (2n) in 87%
yield.
Recycling of the catalyst
The recovery and reusability of the catalyst was assessed
under the optimal reaction conditions as described in the
model reaction. After the completion of reaction, the cat-
alyst was easily separated from the reaction mixture by a
strong external permanent magnet, followed by washing
with Et2O to remove residual product, dried under vacuum,
and then reused directly for the next cycle without further
purification. The results showed that the catalyst could be
recycled and reused for eight times without a significant
reduction in catalytic activity (Fig. 1). The metal leaching
in the catalyst was determined by ICP-MS analysis and
indicated that the Mo and Fe contents were only 0.22 and
0.28 ppm, respectively, in the clear filtrate. These results
certified that the magnetic nano-catalyst applied in this
reaction might have slight loss during the work-up stage. In
order to prove the heterogeneous nature of the catalyst, the
catalyst was separated from reaction liquid using a strong
external permanent magnet in the middle time, approxi-
mate 50% conversion. The reaction process will continue
to be monitored after removal of the catalyst. After a long
time (2.5 h), no further improvement of the yield of pro-
duct was found. All above could be confirmed that MNGO-
supported Mo catalyst had a certain chemical stability
under the reaction conditions and no leaching of the active
species from the support.
Conclusion
In conclusion, we have developed a practical protocol for
ring opening of epoxides to yield b-hydroxyhydroperox-
ides. The procedure displayed many advantages, such as
broad substrate scope, high yield, short reaction times, and
mild reaction condition. Furthermore, the magnetical nano-
graphene oxide-supported molybdenum (Fe3O4/GO-Mo)
catalyst could be readily recovered by applying an external
magnet and recycled several times without considerable
loss of its catalytic activity. It could be predicted that the
present catalyst would be considered as a great potential
alternative for industrial application in the future.
1
products (2e). The structure of 2e was confirmed by H
NMR, 13C NMR with the assistance of DEPT and HMQC
experiments. On the other hand, in the case of glycidyl
ethers (Table 2, entries 6–12), the ring opening might be
attacked predominantly by hydrogen peroxide group on the
terminal carbon atom of the epoxide with less sterically
hindered, which is in accordance with an SN2 reaction
mechanism. It was noted that 2-substituted alkylepoxides
afford slightly lower yields and required longer reaction
time (Table 2, entries 11 and 12). Moreover, with cyclo-
hexene oxide, the ring opening underwent completely via a
trans stereospecific pathway to provide only the trans
isomer (Table 2, entry 13). And symmetrical 2,3-disubsti-
tuted epoxide (entry 14) was also suffered to ring opening
with H2O2 under same experimental conditions and
Experimental
All commercially available chemicals and solvents were
used as received without further purification. Ethereal
hydrogen peroxide (EHP) was prepared by extracting the
commercially obtainable aqueous H2O2 with Et2O
123

Y.-H. Liu et al.
Table 2 Synthesis of b-
hydroperoxy alcohols
aIsolated yield
123

Magnetic nano-graphene oxide-supported molybdenum (Fe3O4/GO-Mo) as a green, efficient…
1-Hydroperoxy-3-methoxy-1-phenylpropan-2-ol
(2e, C10H14O4)
ꢀ
Colorless oil; IR (KBr): m = 3490, 3038, 2924, 1602, 1401,
1
1117 cm-1; H NMR (CDCl3, 500 MHz): d = 7.40–7.36
(m, 5H), 5.04 (d, J = 5.5 Hz, 1H), 4.18 (dd, J = 5.5,
11.0 Hz, 1H), 3.47-3.46 (d, J = 5.0 Hz, 2H), 3.38 (s, 3H),
3.3 (s, 1H) ppm; 13C NMR (CDCl3, 125 MHz): d = 59.2,
71.2, 72.8, 87.9, 127.7, 128.6, 136.5 ppm.
Acknowledgements We are grateful for the financial support from
the National Natural Science Foundation of China (21677046), the
Natural Science Foundation of Hebei Province (H2015206393) and
the Natural Science Foundation of Hebei Education Department
(QN2014126).
References
Fig. 1 Reusability of the catalyst (Fe3O4/GO-Mo) in the model
reaction
1. Chen D, Feng H, Li J (2012) Chem Rev 112:6027
2. Geim K, Novoselov KS (2007) Nat Mater 6:183
3. Park S, Ruoff RS (2009) Nat Nanotechnol 4:217
4. Chua CK, Pumera M (2014) Chem Soc Rev 43:291
5. Dreyer DR, Park S, Bielawski CW, Ruoff RS (2010) Chem Soc
Rev 39:228
6. Wang D, Astruc D (2014) Chem Rev 114:6949
7. Li BL, Zhang M, Hu HC, Du X, Zhang ZH (2014) New J Chem
38:2435
8. Zhao XN, Hu GF, Tang M, Shi TT, Guo XL, Li TT, Zhang ZH
(2014) RSC Adv 4:51089
9. Li BL, Hu HC, Mo LP, Zhang ZH (2014) RSC Adv 4:12929
10. Zhang HY, Hao XP, Mo LP, Liu SS, Zhang WB, Zhang ZH
(2017) New J Chem 41:7108
referring to a literature procedure [37]. Fe3O4/GO-Mo NPs
catalyst was synthesized and characterized according to our
previously reported method [41]. Melting points were
determined using an X-4 apparatus. Elemental analyses
were taken on a Vario EL III CHNOS elemental analyzer.
IR spectra were recorded in the range 4000–600 cm-1
either as neat for liquid or KBr pellets for solid samples
using a Bruker-TENSOR 27 spectrometer instrument.
NMR spectra were run on a Bruker DRX-500 spectrometer
at 500 MHz (1H) and 125 MHz (13C) using CDCl3 as the
solvent with TMS as internal standard.
11. Verma S, Verma D, Jain SL (2014) Tetrahedron Lett 55:240
12. Elazab HA, Siamaki AR, Moussa S, Gupton BF, El-Shall MS
(2015) Appl Catal A Gen 491:58
13. Li XY, Wang X, Song SY, Liu DP, Zhang HJ (2012) Chem Eur J
18:7601
General procedure for synthesis of b-
hydroxyhydroperoxides
14. Gu XD, Zhang WJ, Salomon RG (2012) J Org Chem 77:1554
15. Yaremenko IA, Vil VA, Demchuk DV, Terent’ev AO (2016)
Beilstein J Org Chem 12:1647
16. Zhang M, Han Y, Niu J-L, Zhang Z-H (2017) Adv Synth Catal.
https://doi.org/10.1002/adsc.201700671
17. Maurya R, Soni A, Anand D, Ravi M, Raju KS, Taneja I, Naikade
NK, Puri SK, Kanojiya S, Yadav PP (2013) ACS Med Chem Lett
4:165
18. Zizak Z, Juranic Z, Opsenica D, Solaja BA (2009) Investig New
Drug 27:432
19. Terzic N, Opsenica D, Milic D, Tinant B, Smith KS, Milhous
A mixture of epoxide (1 mmol), 20 mg Fe3O4/GO-Mo
(0.02 mmol of Mo) in 5 cm3 ethereal H2O2 solution (ca.
1.0 mol dm3), was stirred at room temperature for an
appropriate time. The progress of the reaction was followed
by TLC. After completion of the reaction, the catalyst was
separated from the solution by a permanent magnet
(0.5–0.7 T), then washed with Et2O, air-dried, and saved
for the next round of reactions. After that, 20 cm3 Et2O was
added to the reaction mixture and then washed with 5 cm3
H2O. The aqueous layer was back-extracted with EtOAc
(3 9 20 cm3). The combined organic layers were washed
in turn with water (2 9 10 cm3) and brine (2 9 10 cm3),
dried over anhydrous MgSO4, and concentrated under
reduced pressure. The crude product was purified by flash
column chromatography on silica gel (n-hexane/EtOAc) to
obtain the pure b-hydroxyhydroperoxides.
ˇ
WK, Solaja BA (2007) J Med Chem 50:5118
20. Opsenica D, Dennis K, Wilbur M, Solaja B (2003) J Serb Chem
Soc 68:291
ˇ
21. Solaja BA, Terzic N, Pocsfalvi G, Gerena L, Tinant B, Opsenica
´
D, Milhous WK (2002) J Med Chem 45:3331
22. Kirchhofer C, Vargas M, Braissant O, Dong Y, Wang X, Ven-
nerstrom JL, Keiser J (2011) Acta Trop 118:56
23. Ravi M, Anand D, Maurya R, Chauhan P, Naikade NK, Shukla
SK, Yadav PP (2013) Synlett 24:173
24. Wu Y, Li Y, Wittlin S (2012) Heterocycles 84:1217
25. Tada N, Cui L, Okubo H, Miura T, Itoh A (2010) Chem Commun
46:1772
26. Amewu R, Gibbons P, Mukhtar A, Stachulski AV, Ward SA, Hall
C, Rimmer K, Davies J, Vivas L, Bacsa J, Mercer AE, Nixon G,
Stocksb PA, O’Neill PM (2010) Org Biomol Chem 8:2068
Except for compound 2e, all products are known com-
pounds. The physical and spectroscopic data for all known
compounds were found to be identical to those described in
the literature.
123

Y.-H. Liu et al.
¨
27. Griesbeck AG, Schlundt V, Neudorfl JM (2013) RSC Adv 3:7265
28. Orfanopoulos M, Alberti M (2010) Synlett 2010:999
40. Zhang M, Liu P, Liu YH, Shang ZR, Hu HC, Zhang ZH (2016)
RSC Adv 6:106160
´
¨
29. Sabbani S, Pensee LL, Bacsa J, Hedenstrom E, O’Neill PM
41. Zhang M, Liu YH, Shang ZR, Hu HC, Zhang ZH (2017) Catal
Commun 88:39
42. Lu J, Ma EQ, Liu YH, Li YM, Mo LP, Zhang ZH (2015) RSC
Adv 5:59167
(2009) Tetrahedron 65:8531
30. Griesbeck AG, El-Idreesy TT, Lex
62:10615
J
(2006) Tetrahedron
31. Chen HJ, Hao HD, Wu YK (2015) Eur J Org Chem 2015:4423
32. Singh C, Malik H (2005) Org Lett 7:5673
33. Subramanyam V, Brizuela CL, Soloway AH (1976) J Chem Soc
Chem Commun 13:508
34. Ogata Y, Sawaki Y, Shimizu H (1978) J Org Chem 43:1760
35. Tang Y, Dong Y, Wang X, Sriraghavan K, Wood JK, Venner-
strom JL (2005) J Org Chem 70:5103
43. Li XT, Liu YH, Liu X, Zhang ZH (2015) RSC Adv 5:25625
44. Hu HC, Liu YH, Li BL, Cui ZS, Zhang ZH (2015) RSC Adv
5:7720
45. Liu YH, Wang P, Cheng GT (2013) Monatsh Chem 144:191
46. Liu YH, Li L (2012) J Heterocycl Chem 49:861
47. Liu YH, Tao XY, Lei LQ, Zhang ZH (2009) Synth Commun
39:580
36. Li Y, Hao HD, Wu Y (2009) Org Lett 11:2691
37. Li TS, Zhang ZH, Liu YH (2008) Synthesis 2008:3314
38. Yan X, Qiao CH, Guo ZW (2013) Synlett 24:502
39. Li PH, Li BL, An ZM, Mo LP, Cui ZS, Zhang ZH (2013) Adv
Synth Catal 355:2952
48. Liu YH, Liu QS, Zhang ZH (2009) Tetrahedron Lett 50:916
49. Liu YH, Liu QS, Zhang ZH (2008) J Mol Catal A Chem 296:42
50. Zhang ZH, Liu YH (2008) Catal Commun 9:1715
123