A graphene/hemin hybrid material as an efficient green catalyst for stereoselective olefination of aldehydes

Article abstract of DOI:10.1039/c5ra19466k

A hemin/graphene composite, prepared by mixing an aqueous solution of graphene oxide (GO) with hemin and sonicating the suspension for 5 h at room temperature, was investigated for olefination of aldehydes using ethyl diazoacetate in the presence of triphenylphosphine. Efficient olefination of aromatic aldehydes with high (E)-selectivity was obtained, revealing that rGO/hemin is a promising heterogeneous catalyst for the olefination reaction. The as-synthesized catalyst could easily be recovered from the reaction mixture and was subsequently used for several runs without any significantly loss in activity and selectivity.

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Graphene/hemin hybrid material as efficient green catalyst for
stereoselective olefination of aldehydes
Chetan Joshi,a Pawan Kumar,a Babita Behera,b Alexandre Barras,c Sabine Szunerits,c Rabah
Boukherroubc* and Suman L. Jaina*
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
45 nitric oxide, carbon dioxide, hydrogen peroxide and the
oxidation of peroxynitrite.5 However, a serious drawback of
hemin is its high instability due to oxidative degradation. It
Hemin/graphene composite, prepared by mixing an
10 aqueous solution of graphene oxide (GO) with hemin and
sonicating the suspension for 5h at room temperature,
was investigated for olefination of aldehydes using ethyl
diazoacetate in the presence of triphenylphosphine.
Efficient olefination of aromatic aldehydes with high (E)-
15 selectivity was obtained, revealing that rGO/hemin is a
promising heterogeneous catalyst for olefination
reaction. The as-synthesized catalyst could easily be
recovered from the reaction mixture and was
subsequently used for several runs without any
20 significantly loss in activity and selectivity.
undergoes
a
selfꢀoxidation into an inactive mesoꢀ
hydroxyporphyrin form.6 Thus, a great number of efforts are
50 being focused towards the structural modification of hemin
in order to prevent its selfꢀdegradation.7 Although these
modifications increase its activity and stability, they
concurrently enhance synthetic difficulties and cost which
make their utility limited for large scale applications.
55 Alternatively, immobilization of hemin molecules to support
materials constitutes a logical and promising approach to
prevent their selfꢀdegradation. Furthermore, covalent or
strong interaction of metalloporphyrin molecules to the
support is advantageous as it prevents leaching and makes
60 the catalyst more stable.
Introduction
Graphene, a two dimensional single layered structure
consisting of sp2ꢀbonded carbon atoms has several
distinctive properties such as extremely high electronic
conductivity, superior mechanical strength, large surface
65 area and highly conjugated structure.8 Owing to
extraordinary physicochemical and structural properties, it
has extensively been used as support for immobilizing
organic and inorganic catalysts. The potential of graphene
and reduced graphene oxide (rGO) to support organic
70 molecules such as hemin and other porphyrin species
through π–π stacking interactions has widely been
investigated for electrocatalytic applications.9 However,
their use as heterogeneous catalyst for organic
transformations are rarely known.
Olefination or construction of C=C double bonds is one of
the most important transformations in synthetic organic
chemistry. The Wittig reaction1 is the most commonly and
25 widely used approach for constructing carbonꢀcarbon double
bonds for a variety of applications. To avoid the basic
conditions required for the generation of phosphorane
precursors, an alternative methodology using easily
accessible diazo compounds in the presence of metal
30 complexes as catalysts has received considerable interest in
recent decades.2 Among the known metal complexes, iron
macrocyclic complexes particularly iron porphyrins,
phthalocyanines, and corroles displayed good catalytic
activity for this olefination reaction.3 However, these
35 catalysts suffer from the obvious drawbacks of the
homogeneous catalysts such as difficult separation/recovery
as well as nonꢀ recycling ability of the catalyst.
Hemin, a wellꢀknown porphyrinato iron complex, regarded
as an active centre of various heam proteins such as
40 hemoglobin, myoglobin etc,4 plays a vital key role in
biochemical reactions and electronꢀtransport chain. In
addition, it has extensively been used as catalyst for various
potential applications mainly related to environment and
energy issues such as electrochemical reduction of nitrite,
75
In continuation of our onꢀgoing studies towards
developing grapheneꢀbased hybrid catalysts for organic
transformations, herein we report hemin functionalized
reduced graphene oxide (rGO/hemin) hybrid material as an
effective catalyst for olefination of aldehydes using ethyl
80 diazoacetate (EDA) in presence of triphenylphosphine (TPP)
as reducing agent (Scheme 1). The developed
a
heterogenized catalyst displayed comparable catalytic
activity to the homogeneous iron porphyrin catalyst with the
additional benefits of facile recovery and recycling (Table 1,
85 entry 12).
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crumpled and erupted structure in the SEM image suggested
30 the presence of reduced graphene oxide in rGO/hemin
catalyst (Fig. 2a). EDX pattern of the synthesized composite
confirmed the presence of iron (Fig. 2b). Further elemental
mapping indicated the homogeneous distribution of iron
throughout the catalyst (Fig. 2c, 2d).
Scheme 1: Olefination of aldehydes
5
Results and discussion
Synthesis and characterization of the catalyst
Hemin (metalloporphyrin) being a flat molecule can readily
be immobilized on the surface of rGO through π–π stacking
and Hꢀbonding interactions.10 The structure of rGO/hemin
10 catalyst is illustrated in Scheme 2.
35
Fig. 2: rGO/hemin catalyst a) FEꢀSEM image, b) EDX pattern, and
elemental mapping for (c) C, and d) Fe atoms.
.
The UV/Vis absorption spectra of hemin and rGO/hemin
hybrid are displayed in Fig. 3. The spectrum of hemin in
40 DMF shows characteristic absorption peaks i.e a strong
absorption peak at 398 nm attributed to the Soret band and a
broad hump between 450 and 650 nm corresponding to the
Qꢀbands. The UV/Vis spectrum of rGO/hemin hybrid
dispersed in DMF exhibits a broad absorption peak below
45 and above 400 nm due to the ring πꢀπ* transitions of the
Soret band of incorporated hemin. The changes observed in
the Soret band in rGO/hemin hybrid confirmed the
incorporation of hemin molecules within the rGO network.13
Scheme 2: Schematic illustration of rGO/hemin catalyst.
The detailed characterization of the synthesized material was
15 reported in our previous report.11 The incorporation of
hemin onto rGO surface was confirmed by FTIR
measurements (Fig. 1). The FTIR spectrum of hemin (Fig.
1a) showed characteristic absorption peaks at 1580–1600
cmꢀ1 (benzenoid ring stretch) and 1100–1200 cmꢀ1 (pyrrole
20 vibration). The appearance of these characteristic bands in
the FTIR spectrum of rGO/hemin clearly indicated that
hemin molecules were successfully integrated to the rGO
support.12
50
Fig. 3: UVꢀVis spectra of a) hemin and b) rGO/hemin
Thermal stability of the synthesized materials was examined
by thermogravimetric analysis (TGA) (Fig. 4). The TGA
profile of rGO showed initial weight loss between 100ꢀ150
oC probably due to the evaporation of adsorbed water and
25
Fig. 1: FTIR spectra of a) hemin and b) rGO/hemin.
55 solvent molecules. A very small weight loss between 400ꢀ
600 oC was observed due to the loss of residual oxygen
The morphology of the synthesized rGO/hemin catalyst was
investigated using FEꢀSEM (Fig. 2). The appearance of
2
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carrying functionalities (Fig. 4a). In case of free hemin, a
sharp weight loss occurred in the temperature range of 350ꢀ
380 oC probably due to the degradation of the porphyrin ring
structure (Fig. 4b). In contrast rGO/hemin hybrid exhibited
two major weight losses; the first in the range of 100ꢀ150 oC
due to adsorbed water molecules and another at 350 C due
to the degradation of the macrocyclic ring structure of the
hemin (Fig. 4c).14
yield while the selectivity of the product remained
40 unchanged. The reaction was found to be very slow at room
temperature (Table 1, entry 9); the best results were obtained
o
using toluene as solvent at 80 C (entry 4). Further increase
5
of the temperature to 100 °C did not show any significant
enhancement in the conversion as well as selectivity (entry
45 10). Moreover, no reaction occurred when rGO was used as
catalyst under described experimental conditions (Table 1,
entry 11).
o
The iron content in the synthesized hybrid was found to be
10 6.8 wt % or 1.21 mmol/g cat as determined by ICPꢀAES
analysis.
Table 1: Olefination of benzaldehyde under different reaction
conditions[a].
COOC2H5
CHO
COOC2H5
rGO/hemin (cat), 80o
12h, N2
C
+
+
+ PPh3
EDA
cis-
Toluene
trans-
50
Entry
Solvent
Catalyst Temperature Yield E/Z ratioc
amount
(oC)
(%)b
(mol%)
1
2
3
4
5
6
7
8
9
THF
DMF
DCE
1
1
1
1
1
1
2
5
1
1
1
1
70
80
80
80
80
80
80
80
25
100
80
80
61
80
78
92
ꢀd
3:1
3:1
2.5:1
4:1
ꢀ
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
ꢀe
ꢀ
93
93
52
94
ꢀf
4:1
4:1
4:1
4:1
ꢀ
10
11
12
93g
4:1
aReaction condition: benzaldehyde (1 mmol), EDA (1.2 mmol);
b
c
PPh3 (1.1 mmol) under N2 atmosphere; Isolated yield; determined
by H NMR; din the absence of catalyst; in the absence of PPh3;
1
e
fusing rGO as catalyst; gusing homogeneous iron(II) porphyrin as
Fig. 4: DTꢀTGA thermograms of a) rGO, b) hemin and c)
rGO/hemin
55 catalyst.
To explore the scope of this reaction, a number of aldehydes
were subjected to olefination under described reaction
conditions (Table 2). As shown, all the substituted aldehydes
reacted smoothly and gave the corresponding olefination
60 products in moderate to high yields with high transꢀ
selectivity. In general, among all the tested aryl aldehydes
those containing electronꢀdonating groups (Table 2, entries
2−5) were found to be comparatively more reactive and gave
the desired olefin in high yields (85−94 %). Furthermore, the
65 steric hindrance at orthoꢀposition of aryl aldehydes (Table 2,
entry 4) lowered the yield as well as transꢀselectivity of the
product. Interestingly, in case of benzaldehydes having
electron withdrawing substituents the selectivity pattern of
the product was found to be reversed and cisꢀolefins were
70 formed predominantly (Table 2, entries 6ꢀ8). The exact
reason for reversed regioselectivity in case of electron
withdrawing substrates is not clear at this stage. A literature
report by Shindo et al.15 suggested that the E/Z selectivity in
the olefination reaction is strongly dependent on the
75 electronic nature of the paraꢀsubstituents. An increase of
electron density on the phenyl substituents tends to increase
the Eꢀselectivity. However, the electron withdrawing
substituents (particularly –NO2 group) tend to give Zꢀolefins
predominantly.
15 Catalytic activity
The catalytic activity of the rGO/hemin composite was
investigated for the olefination of aldehydes using ethyl
diazoacetate (EDA) in the presence of triphenylphosphine
(PPh3). At first the olefination of benzaldehyde (1 eq) with
20 EDA (2 eq) in the presence of PPh3 (1.1 eq) and rGO/hemin
(1 mol %) was performed in toluene at 80 °C for 12 h. The
reaction was found to occur efficiently and afforded
olefination product in 92 % isolated yield with good transꢀ
selectivity (Table 1, entry 4). In a control blank experiment,
25 no olefination product was obtained in the absence of the
catalyst (Table 1, entry 5). The presence of PPh3 was found
to be vital and in its absence conversion of benzaldehyde
was not observed even after a prolonged reaction time
(Table 1, entry 6). We also investigated the effect of various
30 solvents such as toluene, dimethylformamide (DMF),
dichloroethane (DCE) and THF on the reaction efficiency
(Table 1, entries 1ꢀ4). Among all the solvents studied,
toluene was found to be optimum for this chemical
transformation. To establish the effect of catalyst amount on
35 the product yield, we performed olefination of benzaldehyde
under identical conditions by varying the catalyst amount
from 1 to 5 mol % (Table 1, entries 4, 7ꢀ8). With increasing
the amount of the catalyst, there was a slight increase in the
80 Highly hindered substrate like 2,4,6ꢀtrimethylbenzaldehyde
did not give any product under the described reaction
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conditions (Table 2, entry 9). Similarly, under the same
reaction conditions, 4ꢀdimethylamino benzaldehyde gave
poor product yield (Table 2, entry 10). This lower yield
might be due to the axial coordination of the amino group in
4ꢀdimethylamino benzaldehyde. Alicyclic aldehyde such as
cyclohexane aldehyde reacted efficiently and gave higher
yield of the desired olefin (Table 2, entry 11).
30 charged with substrates i.e. benzaldehyde (1 mmol), Ph3P
(1.1 mmol) and EDA (1.2 mmol) and continued the reaction
under refluxing condition for 12 h. No conversion of
benzladehyde was observed, which indicated that the
developed catalyst was quite stable and did not show any
35 leaching. These findings further establish the truly
heterogeneous nature of the rGO/hemin catalyst.
5
Table 2: rGO/hemin catalyzed olefination of aldehydes.a
Entry Substrate
Product
Yield E/Z
(%)[b] ratio[c]
COOC2H5
1
92
7:1
COOC2H5
COOC2H5
CHO
+
COOC2H5
2
94
4:1
CHO
+
COOC2H5
3
4
93
87
5:1
3:1
COOC2H5
COOC2H5
CHO
+
COOC2H5
+
CHO
COOC2H5
5
6
93
85
5:1
1:4
COOC2H5
Fig. 5: Recycling experiments.
MeO
CHO
+
COOC2H5
+
MeO
MeO
To investigate the structural and chemical changes of the
40 rGO/hemin catalyst after catalysis, the recovered catalyst
after the fifth recycling run was characterized with FTIR,
SEM, UV and TGA (Fig. 6). FTIR spectrum of the recycled
catalyst showed similar bands like the freshly synthesized
catalyst (Fig. 6a). Similarly, the crumpled and erupted
45 structure of the recycled catalyst suggested that the
morphology of catalyst remained intact after the catalytic
reactions (Fig. 6b). Also no obvious changes were observed
in the UVꢀvisible spectrum of the recycled catalyst as
compared to that of fresh catalyst (Fig. 6c). Finally, TGA
50 analysis of recycled catalyst (Fig. 6d) suggested that the
recycled catalyst was thermally stable and showed similar
degradation pattern as freshly synthesized catalyst.
COOC2H5
Br
CHO
Br
Br
Cl
COOC2H5
+
7
8
84
65
1:3
1:4
COOC2H5
COOC2H5
Cl
CHO
CHO
Cl
COOC2H5
+
O2N
O2N
O2
N
OMe
CHO
OMe
9
MeO
ꢀ
ꢀ
ꢀ
COOC2H5
+
10
28
3:1
COOC2H5
N
CHO
N
N
COOC2H5
+
CHO
11
92
5:1
COOC2H5
aReaction conditions: aldehyde (1 mmol), EDA (1.2 mmol), Ph3P
10 (1.1 mmol), catalyst (1 mol%, 0.01 mmol), toluene (5 ml) at 80 °C
under N2 atmosphere; bIsolated yields; cE/Z ratio calculated by 1H
NMR.
Reusability of the solid catalyst is one of the most important
criteria to make it viable at an industrial scale. To study the
15 reusability of the heterogeneous rGO/hemin catalyst, the
olefination of benzaldehyde was studied under optimized
reaction conditions. After completion of the reaction, the
catalyst was separated by simple filtration and the recovered
catalyst was used for subsequent five cycles using
20 benzaldehyde as model substrate. In all cases, the product
yield as well as transꢀselectivity of the product remained
almost the same (Fig. 5). These results confirmed that the
developed catalyst was highly stable and can be reused for
several runs without any significant change in its catalytic
25 activity. Moreover, the iron content in the recovered catalyst
after five runs was found to be almost similar (6.5 wt%) to
that of fresh catalyst (6.8 wt%). Furthermore, to ascertain the
leaching, a toluene solution of the catalyst was refluxed for
12 h. After separating the catalyst, the obtained filtrate was
Fig. 6: a) FTIR spectra of rGO/hemin i) fresh catalyst, ii) after five
55 recycling experiments, b) FEꢀSEM image of recovered rGO/hemin,
c) UVꢀVis spectra of rGO/hemin: i) fresh catalyst, ii) after five
recycling experiments, d) TGA thermograms: i) fresh rGO/hemin,
ii) after five recycling experiments.
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40 grade water were purchased from MERCK India. All the
chemicals and solvents were of analytical grade and used as
received.
Although the exact mechanism of the reaction is not clear at
this stage, in analogy to the existing report by Woo et al.,3b,16
it is assumed that the reaction involves the transfer of
carbene generated from ethyldiazoacetate to phosphorous to
give phosphazene in the presence of hemin. In the
subsequent step, the phosphazene reacts with aldehyde to
yield the corresponding olefin in a similar way to Wittig
reaction (Scheme 3).
5
Characterization
45 Fourier Transform Infrared (FTIR) spectra were recorded on
a Perkin–Elmer spectrum RXꢀ1 IR spectrophotometer using
potassium bromide window. UVꢀVisible absorption spectra
of hemin and rGO/hemin in DMF were collected on a Perkin
Elmer lambdaꢀ19 UVꢀVISꢀNIR spectrophotometer using a
50 10 mm quartz cell. Thermal stability of samples was
evaluated by thermogravimetric analyses (TGA) using a
thermal analyzer TAꢀSDT Qꢀ600. Analysis was carried out
in the temperature range of 40 to 800 °C under nitrogen flow
with a heating rate of 10 °C/min. The iron content of the
55 hybrid rGO/hemin catalyst was measured on Inductively
Coupled Plasma Atomic Emission Spectrometer (ICPꢀAES,
DRE, PSꢀ3000UV, Leeman Labs Inc, USA). For ICPꢀAES,
0.05 g of catalyst was leached out using Conc. HNO3 and
final volume was made up to10 ml by adding distilled water.
60 2.2 Synthesis of rGO/hemin nanocomposite11
Hemin functionalized reduced graphene oxide (rGO/hemin)
hybrid was synthesized by following our previously reported
method.11 Graphene oxide was synthesized by following the
modified Hummer’s method.17 For the synthesis of
65 rGO/hemin/catalyst, 0.75 mL (10 mM) of hemin was
10
Scheme 3: Possible mechanism of olefination of aldehydes over
rGO/hemin.
dissolved in DMF which was further added to
a
homogeneous suspension of GO (0.75 mL, 0.5 mg mLꢀ1) in
distilled water and ultrasonicated at 130 kHz in a Fisher,
Loughborough, Leicester, UK Transonic TIꢀHꢀ10
70 ultrasonication bath for 5 h at 50 ºC. The precipitate was
separated by centrifugation at 14000 rpm for 1 h, washed 3
times with water and dried in an oven at 60 ºC for 6 h.
Conclusion
In conclusion, an efficient and simple method has been
15 described for the synthesis of rGO/hemin hybrid by the
treatment of graphene oxide with hemin under
ultrasonication for
5
h. FTIR, UVꢀVis and TGA
measurements confirmed GO reduction and hemin
incorporation to yield rGO/hemin hybrid material. The
20 resulting rGO/hemin was successfully used as a selective
catalyst for the olefination of various aldehydes. The
synthesized catalyst showed the property of both hemin as
well as of graphene. Graphene provided large surface area to
the substrate, supported hemin through πꢀπ interactions, and
25 increased the active sites on the surface. Due to the
synergistic effect of both components, rGO/hemin hybrid
catalyst exhibited high and excellent yields of cinnamates
from the corresponding aldehydes as compared to the well
established homogeneous catalytic systems. Moreover, the
30 catalyst was very stable and can be reused several times
without any activity loss.
2.3 Typical experimental procedure for olefination of
aldehydes
75
In a 10 mL Schlenk tube, placed in a preheated oil bath at
80 ᵒC, was added aldehyde (1 mmol), ethyldiazoacetate (1.2
mmol), triphenylphosphine (1.2 mmol) and catalyst (1 mol
%) in toluene (5 mL) under a nitrogen atmosphere. The
resulting mixture was stirred as indicated in Table 2. After
80 being cooled the mixture at room temperature, the catalyst
was recovered from the reaction mixture via centrifugation.
The obtained filtrate was concentrated under reduced
pressure and purified by column chromatography using
hexane/ethyl acetate (15:1) to give pure olefin. The yields of
85 the isolated products are given in Table 2. The
regioselectivity of the products was determined by 1H NMR.
Experimental
Acknowledgements
Material
Authors are thankful to Director IIP for granting permission
90 to publish these results. PK is thankful to CSIR New Delhi
for providing research fellowship. CJ kindly acknowledges
CSIR, New Delhi for providing technical HR under XII five
year projects. A.B., S.S. and R.B. acknowledge financial
support from the Centre National de la Recherche
95 Scientifique (CNRS), The Lille1 University and the Nord
Graphite flakes, iron protoporphyrin IX (hemin) and
35 hydrazine monohydrate were purchased from Sigmaꢀ
Aldrich. Dichloromethane, potassium permanganate
(99.0%), sodium nitrate (99%), concentrated sulphuric acid,
hydrogen peroxide (30%), hydrochloric acid (35%),
methanol, ethanol, dimethylformamide (DMF) and HPLC
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aChemical Sciences Division, CSIR-Indian Institute of Petroleum,
Dehradun-248005, India
75
5
Tel. 91-135-2525788; Fax: 91-135-2660202; Email:
suman@iip.res.in
bAnalytical Sciences Division, CSIR-Indian Institute of Petroleum,
Dehradun-248005, India
10 cInstitut d'Electronique, de Microélectronique et de
Nanotechnologie (IEMN), UMR CNRS 8520, Université Lille1,
Avenue Poincaré-BP60069, 59652 Villeneuve d'Ascq Cédex, France
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DOI: 10.1039/C5RA19466K
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