One-step synthesis of 2,5-diformylfuran from monosaccharides by using lanthanum(iii) triflate, sulfur, and DMSO

Article abstract of DOI:10.1039/d0cc05582d

The combination of lanthanum(iii) triflate, sulfur, and dimethyl sulfoxide prompted a facile, direct preparation of 2,5-diformylfuran from glucose and fructose. The one-step dehydration/oxidation of fructose afforded 2,5-diformylfuran in an excellent yield with high selectivity. The proposed mechanism, large-scale synthesis, and product separation were presented. This approach represents a straightforward and eco-friendly pathway, which can be applied in the large-scale production of 2,5-diformylfuran from fructose. This journal is

Full text of DOI:10.1039/d0cc05582d

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One-step synthesis of 2,5-diformylfuran from monosaccharides by lanthanum(III) tDriOflI:a1t0e.1,039/D0CC05582D
sulfur, and DMSO
Quynh Nhu Ba Nguyen,a,b Hao Anh Nguyen Le,a,b Phat Duc Ly,a,b Ha Bich Phan,a,b,c Phuong Hoang
Tran a,b*
Affiliations
aDepartment of Organic Chemistry, Faculty of Chemistry, University of Science, Ho Chi Minh City,
721337, Viet Nam.
bVietnam National University-Ho Chi Minh City (VNU-HCM), 721337, Viet Nam.
cInstitute of Public Health, Ho Chi Minh City, 700000, Viet Nam.

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DOI: 10.1039/D0CC05582D
Journal Name
COMMUNICATION
One-step synthesis of 2,5-diformylfuran from monosaccharides by
lanthanum(III) triflate, sulfur, and DMSO
Received 00th January 20xx,
Accepted 00th January 20xx
Quynh Nhu Ba Nguyen,a,b Hao Anh Nguyen Le,a,b Phat Duc Ly,a,b Ha Bich Phan,a,b,c Phuong Hoang
Tran a,b*
DOI: 10.1039/x0xx00000x
www.rsc.org/
two steps, dehydration of monosaccharide (e.g., fructose or
glucose) and oxidation of the intermediate HMF.17-21
facile, direct preparation of 2,5- Cheap and readily available sulfur is an attractive element
A combination of lanthanum(III) triflate, sulfur, and dimethyl
sulfoxide prompted
a
diformylfuran from glucose and fructose. The one-step
dehydration/oxidation of fructose afforded 2,5-diformylfuran in
excellent yield with high selectivity. A proposed mechanism, large-
scale synthesis, and product separation were presented. This
approach represents a straightforward and eco-friendly pathway,
which can be applied in large-scale production of 2,5-
diformylfuran from fructose.
for reactivity as its smaller congener oxygen, acting as
23
oxidant and promoting the oxidative reactions.22,
In
contrast to oxygen, sulfur remains in a solid state at room
temperature; sulfur is a stable, non-volatile, and therefore
easy to work with.24, 25 The melting point of sulfur is lower
o
(115.2 C), and it can act as reaction media in the molten
state.26, 27
Efficient and sustainable synthesis of fuels, polymers, and
chemicals from inexpensive and inexhaustible resources of
carbohydrates has received increasing attention.1-3 5-
Hydroxymethylfurfural (HMF), generated through
dehydration of fructose, is known to be a critical precursor
Previous work 12, 17, 18, 20, 28-30
O
O
HO
selective oxidation
O
dehydration
Fructose
O
O
and platform chemical to link biomass resources with
DFF
HMF
5
sustainable energy and chemical industry.4,
HMF
This work
possesses hydroxyl and aldehyde functional groups, which
can easily be oxidized or reduced to provide a wide range
of chemicals for applications in the synthesis of biofuel,
polymers, and pharmaceuticals.3, 6 2,5-Diformylfuran (DFF),
which can be achieved from HMF via oxidation, has
potential applications in the preparation of
O
La(OTf)3 (2.5 mol%), 150 o
C
O
O
Fructose
S (3.0 mmol), DMSO (2.0 mL)
DFF (up to >99% yield by HPLC)
Scheme 1. Synthesis DFF from fructose.
In current work, we report that the mixture of
lanthanum(III) triflate, sulfur, and DMSO is an efficient,
practical, and straightforward reaction medium in the
direct preparation of DFF from monosaccharides including
fructose and even more challenging glucose substrate.
Notably, DFF was produced with a yield of almost 100% in a
one-step process. Metal triflates have recently attracted
considerable attention because their Lewis acidity is higher
than metal halides.31, 32 Moreover, metal triflates work well
not only in organic solvents but also in aqueous media.33, 34
Recently, there have been numerous reports describing
various useful methods for the direct derivatization of
pharmaceuticals,
organic
conductors,
polymers,
heterocyclic ligands, and luminophores.7-11 The
straightforward conversion of carbohydrates to DFF is
highly attractive due to available and cheap starting
materials.12-16 The one-pot preparation of DFF from
carbohydrates involves a tandem reaction using an acid
catalyst and an oxidative reagent. The procedure comprises
aDepartment of Organic Chemistry, Faculty of Chemistry, University of Science, Ho Chi
Minh City, 721337, Viet Nam.
bVietnam National University-Ho Chi Minh City (VNU-HCM), 721337, Viet Nam.
cInstitute of Public Health, Ho Chi Minh City, 700000, Viet Nam.
All authors contributed equally.
fructose to DFF assisted by either homogeneous or
18-20, 30, 35, 36
heterogeneous catalysts.7,
However, these
Corresponding author: thphuong@hcmus.edu.vn
processes involved two steps as follows: Brønsted acid-
promoted dehydration of fructose into HMF, and formation
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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6.4 44.3
10
H2SO4
H3PO4
-
DMSO
DMSO
DMSO
150
150
150
of DFF through the metal-assisted oxidation of HMF. Up to
now, the use of metal triflate combined with S/DMSO in 11
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DOI: 10.1039/D0CC05582D
0
0
0
0
one-step preparation of DFF from fructose has not been
reported in the literature. The preparation of DFF from
fructose using La(OTf)3 and sulfur in DMSO was reported
herein as a novel “one-pot, one-step” procedure. The high
temperature plays a vital role in the dehydration of
fructose in DMSO.13, 37 Thus, in a preliminary experiment,
fructose (1.0 mmol), La(OTf)3 (2.5 mol%), sulfur (6.0 mmol),
and DMSO (2.0 mL) were heated at 150 °C for 18 h, and
subsequent analysis showed that DFF yield was obtained in
82.8%. Next, the control experiments were carried out in
DMSO (2.0 mL) at 150 °C for 18 h without La(OTf)3 or sulfur.
In both cases, no DFF was detected by HPLC analysis.
Interestingly, a significant improvement of the DFF yield
was achieved in the same condition with the use of both
La(OTf)3 and sulfur, rationalized by the synergistic effects of
combined La(OTf)3 and sulfur (Table 1, entry 4). The
reaction hardly occurred at lower reaction temperatures
(Table 1, entries 1-3). No reaction was observed at room
temperature, at which both oxidation and dehydration are
disfavored, while the progressive formation of HMF was
noted at low temperature. DFF yield was increased by
raising reaction temperature to 150 oC. Thus, the selectivity
to HMF or DFF could be easily tuned by governing the
reaction temperature. The solvent demonstrated a vital
effect on the DFF yields in previous reports.5, 13 Among the
evaluated solvents, DMSO is the best solvent for the
current method (Table 1, entries 5-7). Besides, the yields of
the DFF also decreased when other metal triflates such as
Bi(OTf)3 and Ho(OTf)3 were employed (Table 1, entries 8-9).
The synthesis of DFF was also carried out with Brønsted
acids, including H2SO4 and H3PO4 (Table 1, entry 10-11). We
observed that the reaction using H2SO4 as a catalyst
proceeded with difficulty, affording only 44.3% yield of DFF.
However, the desired product was not detected in the
presence of a catalyst with lower acidity (H3PO4).
12
a
Reaction conditions: Catalyst (2.5 mol%), fructose (1 mmol), S (6
mmol), solvent (2 mL), 18 h. DFF and HMF yields were quantified by
the use of HPLC with an external standard.
Under the optimized conditions, the reaction time effect on
the reaction yield was investigated. The reaction mixture
was heated at 150 C in various periods of time. As plotted
o
in Figure 1, the DFF yields slowly increased at 0-4 h, rapidly
increased at 9-18 h, and obtained 100% DFF yield at 24 h.
The yield variations of HMF and DFF at various periods of
reaction time indicated that the oxidation hardly
proceeded in short reaction time. Next, the amount of
sulfur was tested, and the results were presented in Figure
2. DFF yield increased gradually with the further addition of
sulfur. The best yield of DFF was observed by using 10
mmol of sulfur at 12 h and then kept constant. The results
demonstrate that the current method was affected by the
sulfur loading level.
Fig. 1 The effect of reaction time in the presence La(OTf)3 (2.5
mol%), fructose (1 mmol), S (6 mmol), DMSO (2 mL), 150 oC.
Table 1. Optimization of the reaction condition.a
HO
OH
O
O
O
HO
Catalyst
O
O
O
+
HO
S/DMSO
HO
Fructose
OH
DFF
HMF
Entry
Catalyst
Solvent
Temp.
HMF
yield
0
30.3
64.5
0
DFF
yield
0
(oC)
rt
1
2
3
4
5
6
La(OTf)3
La(OTf)3
La(OTf)3
La(OTf)3
La(OTf)3
La(OTf)3
DMSO
DMSO
DMSO
DMSO
DMF
80
0
120
150
150
150
5.3
82.8
0
0
1.8
Nitrobenzene
1.4
7
8
9
La(OTf)3
Bi(OTf)3
Ho(OTf)3
Dioxane
DMSO
DMSO
150
150
150
0
0
42.7
0
36.5
55.8
Fig. 2 The effect of sulfur loading in the presence La(OTf)3
(2.5 mol%), fructose (1 mmol), DMSO (2 mL), 150 oC.
2 | J. Name., 2012, 00, 1-3
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