Production of 2,5-hexanedione and 3-methyl-2-cyclopenten-1-one from 5-hydroxymethylfurfural

Article abstract of DOI:10.1039/c5gc02493e

A novel approach for the production of 2,5-hexanedione (HDN) and 3-methyl-2-cyclopenten-1-one (3-MCO) from 5-hydroxymethylfurfural (HMF) by water splitting with Zn is reported for the first time. The use of high temperature water (HTW) conditions is the key for the efficient conversion of HMF to HDN and 3-MCO. Parameters regarding the Zn amount, temperature and reaction time are optimized and HDN and 3-MCO are produced in 27.3% and 30.5% yields, respectively. The roles of HTW and ZnO obtained by oxidation of Zn in water for the conversion of HMF, together with intermediate structures, are discussed to understand the mechanism of the reaction.

Full text of DOI:10.1039/c5gc02493e

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Production of 2,5-hexanedione and 3-methyl-2-cyclopenten-1-one
from 5-hydroxymethylfurfural
Dezhang Ren, Zhiyuan Song, Lu Li, Yunjie Liu, Fangming Jin and Zhibao Huo*a
Received 00th January 20xx,
Accepted 00th January 20xx
A novel approach for production of 2,5-hexanedione (HDN) and 3-methyl-2-cyclopenten-1-one (3-MCO) from 5-
hydroxymethylfurfural (HMF) by water splitting with Zn is reported for the first time. The use of high temperature water
(HTW) conditions is key for the efficient conversion of HMF to HDN and 3-MCO. Parameters regarding Zn amount,
temperature and reaction time are optimized and HDN and 3-MCO are produced in 27.3% and 30.5% yields, respectively.
The roles of HTW and ZnO obtained by oxidation of Zn in water for, the conversion of HMF, together with intermediates
structures, are discussed to understand the mechanism of the reaction.
DOI: 10.1039/x0xx00000x
www.rsc.org/
dimethylfuran (DMF)15. However, most of these synthetic
processes are subject to a lot of problems. For example, high
cost of catalysts, corrosiveness of liquid acid or base, toxicity of
1. Introduction
Biomass has long been considered as a promising renewable
resources, and provides an alternative to reduce the
dependence on fossil fuels. The utilization of the bio-platform
molecules converted from biomass to synthesize a number of
organic solvent and heavy metals, and tedious steps are
problems that necessitate solutions. Furthermore, the
feedstocks used in the above processes are derived from crude
oil resources and related substrates. As mentioned above,
utilization of bio-based material to produce cyclopentenones
via green processes is a preferable choice. To the best of our
knowledge, the studies about direct synthesis of
cyclopentenones from bio-based materials, such as HMF have
never been reported.
fuels and chemicals is
a common strategy. HMF (5-
hydroxymethylfurfural) as one of promising platform chemicals
1
selected by US Department of Energy (DOE) , is derived from
dehydration of hexose. Researches have focused on
conversion of HMF to value-added compounds, which is one of
the important fields in green/energy chemistry.
Diketone derivatives including HDN represent an important
class of chemicals because of their wide utility. For example,
they have been used for the synthesis of valuable products
such as alcohols, amines, solvents, surfactants and
cycloketones16-21. Diketone derivatives have also been utilized
recently to prepare pharmaceutical ingredients such as
pyrrolidine.16, 19-21 However, little attention has been paid to
the diketone derivatives, especially HDN produced from HMF.
A problem for the synthesis of HDN from HMF is attributed to
difficulty in precise control of a bifunctional catalytic system,
Cyclopentenones including 3-MCO (3-methyl-2-cyclopenten-
1-one) with α,β-unsaturated carbonyl are not only useful
2
compounds in organic synthesis , but also key intermediates
for the synthesis of natural products such as jasmonoids,
prostanoids, cortisone, muscone, and other bioactive
compounds 3, 4. Over the past few decades, the development
of synthetic methods of cyclopentenones has been reckoned
as a hot topic. In the early stage, Piancatelli et al. synthesized
cyclopentenones from furans, in which the reaction was
catalyzed by a homogenous strong acid in acetone/water
5
which simultaneously contain acid sites for ring-opening of
22
system . Synthetic methods using the other starting materials
7
furan and hydrogenating sites for hydrogenation of HMF
.
such as alkynes, alkenes and carbon monoxide 3, 6, dienones ,
8
9
Liquids acid such as carbonic acid and solid acids such as
Amberlyst-15 were investigated to provide acid site, and noble
metals including Pd and Ir were used for hydrogenation of
HMF 16, 22. However, either no HDN was produced or low yields
were obtained, depending on the conditions, in these
reactions. In addition, H2 has been used as hydrogen donor in
these reactions, while the drawbacks of utilizing H2 exists in
safety risks for its high pressure, flammable characters and
increasing the cost during transportation and handling.
Recently, Tuteja et al. prepared a solid bifunctional catalyst
which deposited Pd over a solid acidic zirconium phosphate to
carry out conversion of HMF to HDN without support of
1,3-dicarbonyl compounds , isoprene , mesyltriflone 10, diazo
ketones 11, alkynones 12, and HDN (2,5-hexanedione) 13, 14 were
also developed. It is worth mentioning that HDN can be
obtained by hydrolysis of HMF-derived product, 2,5-
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hydrogen donor. The highest yield of HDN was 33.7% 23. The were purchased from Aladdin Chemical Reagent. HMF, 3-MCO,
authors interpreted this high yield as the acidity of the (5-methyl-2-furyl) methanol (MFM), 5-methyfurfural (MF) and
zirconium phosphate surface would effectively accelerated the 3-methylcyclopentanone (MCPE) were purchased from Energy
cleavage of C-O bond in a furan ring. However, in the process, Chemical (China). Ni/γ-Al2O3, Ag/SiO2 and porous Ni were
41
noble metal catalyst (Pd/ZrP, which required
a
quite prepared according to the previous procedures40,
. All
complicated synthetic process), organic solvent (ethanol) and chemicals were analytical reagents.
longer time (21 h) were used. Therefore, the development of
new methods for the production of HDN is still highly 2.2 Experimental procedure
desirable.
Most of the experiments were conducted in a Teflon-lined
stainless steel batch reactor whose inner volume was 30 mL.
The amount of HMF was 0.20 mmol in all the experiments.
Metal powder, water and feedstock were sealed into reactor
after air was excluded by purged with nitrogen gas. The sealed
reactor was then placed into a preheated oven. The oven
temperature decreased after the reactor placed in. Hence, the
reaction started when the oven temperature reached up to
desired value. After the desired time, the reactor was moved
out and cooled down to room temperature.
Simultaneous production of HDN and 3-MCO from HMF
seems to be a green strategy. However, this method has never
been reported in previous studies so far. High temperature
water (HTW) as reaction medium is a promising method, for
the inherent characters of HTW including high ionization
constant (Kw), which makes it possible to carry out acid/base
catalytic reactions 24-26, and has attracted attention in energy
and chemical industry. In addition, water is considered as a
green hydrogen donor to participate hydrogenation and
hydrogenolysis reactions 25, 27-32. Other than that, water is one
of the safest and cleanest solvents, abundant and widespread
in nature.
Other experiments with H2 as hydrogen source were
performed in a SUS316 stainless steel tube whose inner
volume was 5.7 mL. Metal or metal oxide powder, catalyst,
water and feedstock were added into this tube. After purged
by H2, it was pressured with H2 to 3 MPa. The sealed tube was
then placed into salt bath at 250 oC. After the reaction was
over, the tube was cooled in water
33-35
Our group have focused on the conversion of biomass
into value-added chemicals for many years. Among some of
these researches, it has been clarified that hydrogen can be
28, 30, 31, 36
generated in situ by oxidizing cheap metals in water
.
More recently, we have investigated copper-based catalysts
for hydrogenation of glycolide and lactic acid into diols; and
Liquid sample was filtered with 0.45 μm syringe filter and
collected into a vial for analysis. Solid sample was washed with
ethanol and water for several times, and dried at 60 oC for
overnight.
Pd/C catalyst for the conversion of glucose into diol. In both
32, 37,
cases good results were obtained
38. Excitingly, the
studies by some research groups 39, who reported that ZnO
can be reduced to metallic Zn by solar energy, makes our
studies more meaningful.
2.3 Products analysis
GC-FID (gas chromatography with flame ionization detector,
Agilent GC7890A) and GC-MS (gas chromatography with mass
spectrometer, Agilent GC7890A- MS5975C) were performed to
analyze liquid samples, which equipped with HP-Innowax
column (30 m × 0.25 mm × 0.25 µm). Solid samples were
analyzed by XRD (X-ray diffraction, Shimadzu 6100) and the
amount of oxidized Zn was also determined by XRD. The HMF
conversion and product yield were defined by the following
equations shown in Eqs 1 and 2.
Inspired by these findings, we here for the first time, report
a novel approach for production of HDN and 3-MCO from HMF
by water splitting with Zn. The main strategy is illustrated in
Scheme 1.
2. Experimental
2.1 Experimental materials
Fe, Mn, Mg, Al, Zn, Ni, Cu, ZnO, Cu2O, CuO, ZrO2, Al/Ni alloy,
HCOOH, NaOH, furfural and furfuryl alcohol were all purchased
from Sinopharm Chemical Reagent (China). Pd/C and HDN
3. Results and discussion
3.1 Active metal screening
As is well known, some active metals, such as Fe 27, 42, Mn 28,
31, Al and Mg 28, 32, can react with HTW to produce hydrogen to
induce the hydrogenation reaction. A series of experiments
were performed to investigate the effect of active metals for
the conversion of HMF. After the reactions, the XRD analysis in
Figures SI-1a, 1b and 1c showed that Fe and Al still remained
unchanged and Mn and Mg were completely oxidized at 250
oC. One of the reasons for non-oxidation of Fe and Al is that
Scheme 1. The main strategy for the conversion of HMF.
2 | J. Name., 2012, 00, 1-3
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the temperature of 250 oC is too low to enable water to 3.2 Effect of parameters
possess enough thermal energy for oxidation of Fe28 and Al
Various conventional catalysts were investigated to improve
the yields of products, and the results shown in Table SI-2
indicated that extra added catalysts did not improve the
conversion of HMF into HDN and 3-MCO.
leading to generation of hydrogen. From Table SI-1, it is clear
that no desired compounds were observed after the reaction
when Fe, Mn, Al and Mg were used as reductants, although
HMF was completely consumed in this process (entries 2-5). It
was thought that HMF was decomposed completely under the
reaction conditions to give a complex mixture of products.
However, the use of Zn was effective for the conversion of
HMF, and the yields of HDN of 21.3%, 3-MCO of 19.7%, MF of
4.3% and MCPE of 1.0% were obtained, respectively (entry 1).
With regard to hydrogenation and hydrogenolysis reactions,
H2 partial pressure is a vital factor for adjusting reaction rate
and selectivity 16, 22. Thus, selecting proper amount of Zn is a
manner to control the H2 pressure. Figure 1 shows the
influence of the amount of Zn with corresponding theoretical
partial pressure of H2 marked below at 25 oC in HMF
conversion with 7.5 mL H2O. The HMF conversion was
To investigate the effect of reaction time for HMF
conversion, a series of experiments were performed by
changing reaction time at 250 oC. The yields/conversions of
products confirmed by GC-MS were plotted in Figure 2. HMF
could be rapidly consumed at the first 40 min and HMF
conversion was 97.3%. The yield of HDN with the average
growth rate of 25.2%/h increased rapidly, and then the
average rate slowed down to 5.1%/h from 40 to 140 min. The
highest HDN yield of 27.3% was achieved at 140 min, and then
decreased slowly with the average decrease rate of 1.2%/h.
Similarly, the average growth rate of 3-MCO was 15.8%/h at
first 100 min, and then decreased to 0.9%/h from 100 to 480
min. The highest yield of 3-MCO was up to 30.5%. The yield of
MFM was 9.4% at first 10 min, and exhausted quickly. Also the
yield of MF increased at first, and then gradually decreased.
The yield of MCPE kept at a low level during the reaction.
approximately 90% when
5 mmol Zn was used with
corresponding H2 pressure of 0.55 MPa. The HMF was
completely converted when the amount of Zn was increased
to exceed 15 mmol with the corresponding H2 pressure of 1.65
MPa. The results indicate that the HMF can be easily converted
by in-situ hydrogen even with low amounts of Zn. The yield of
MF decreased with the Zn amount changed from 5 to 35
mmol, and with corresponding H2 pressure changed from 0.55
to 3.85 MPa. The decreasing yield of MF might be owing to the
decomposition of MF caused by redundant Zn. Both HDN and
3-MCO yields increased as the Zn amount increased from 5 to
25 mmol, and then decreased when amount of Zn exceeded 25
mmol, and the maximum values of 21.3% of HDN and 19.7% of
3-MCO were obtained, respectively. It means that the amount
of Zn exerts influence on the HMF conversion to HDN and 3-
MCO. In addition, as a product that can be generated by
hydrogenation of 3-MCO, MCPE consistently maintained a low
yield; indicating that in-situ generated hydrogen has a little
effect impact on production of MCPE.
Figure 2. Effect of time for the conversion of HMF (0.20 mmol
HMF, 25 mmol Zn, 7.5 mL H2O, 250 oC)
100
80
100 o
150oC
C
200 o
250 o
C
C
60
40
20
0
36.2%
25.9%
16.8%
6.1%
0
1
2
3
4
5
6
12
13
14
15
16
Reaction time (h)
Figure 1. Effect of the amount of Zn (0.20 mmol HMF, 7.5 mL
H2O, 250 oC, 60 min)
Figure 3. The change of the amount of Zn during the reaction
at different temperature (25 mmol Zn, 7.5 mL H2O)
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Reaction temperature is also an important factor for water 3.3 Possible catalytic activity of ZnO formed in situ
possessing acid/base catalytic activity 25, which is closely
To investigate the effect of ZnO formed during the reaction,
connected in furan ring-opening/rearrangement process. HMF
conversion was monitored at 100 oC (see Figures SI-2 and SI-3)
two comparative experiments were conducted for the
conversion of HMF by the addition of 3 MPa gaseous hydrogen
with two kinds of ZnO; one was formed by Zn oxidation in
water and another commercial one. As shown in Table SI-3,
only a low yield of MF was obtained and no other products
were detected, although the conversion of HMF was
approximately 60% (entries 1-2). It indicates that the gaseous
hydrogen is ineffective and in-situ hydrogen generated by
oxidation of Zn in water plays an important role for the
conversion of HMF. Furthermore, when ZnO was not added,
no desired products but black humins were obtained (entry 3).
It might be thought that hydrogen generated in situ from Zn
oxidation is active for the hydrogenation/hydrogenolysis
reactions, while the externally supplied hydrogen is not30, 36, 43,
44. As mentioned later, self-aldol condensation of HDN to 3-
MCO are catalyzed by ZnO. Hence, we suggested that obtained
ZnO exhibited catalytic performance to promote the
conversion of HMF or formed intermediates in the process.
With optimized conditions in hand, two substrates, furfural
and furfuryl alcohol, with similar structure as MF and MFM to
synthesize cyclopentenone was also proved to be feasible. The
results of Table SI-4 and Figure SI-6 indicated that furfuryl
alcohol provided higher yield of cyclopentenone than that of
furfural.
o
and 150 C (see Figures SI-4 and SI-5). Although the oxidation
of Zn at 100 and 150 oC was much slower than at 250 oC
(Figure 3), HMF was completely converted in a short time.
However, the yields of HDN and 3-MCO at 100 oC were only
around 14% and 5%, respectively, even when the reaction time
was prolonged to 10 h. The strong signal of MFM was found at
15 h, which seemed to be an intermediate. It seems that the
lower temperature leads to low acid catalytic ability and low
thermal energy of water, although both of which should be
high enough to promote the MFM ring opening process. The
HDN yield of 20.1% and the 3-MCO yield of 9.9% were
o
obtained at 150 C, which were still much lower than those at
250 oC. These results indicate that higher temperatures
contributed to the efficient conversion of HMF.
In general, hydrogen production depends on the
temperature of oxidation of Zn in water. To better understand
the hydrogen production during the reaction, the remaining
percentage of Zn in solid residue after the reaction was
investigated by XRD at different temperatures as shown in
Figure 3. When the temperature was 100 oC, the amount of Zn
decreased slowly to 36.2% between 0 and 13 h, and kept
unchanged after 13 h. Perhaps, an oxide film would be formed
on the surface of Zn which would inhibit further oxidation of
.
Zn, leading to
a low hydrogen production. When the
4. Mechanistic Studies
temperature was at 150 oC, the reaction between Zn and HTW
was accelerated and the rest of Zn was 25.9% after 5 h. The
higher temperatures such as 200 and 250 oC showed the faster
oxidation of Zn, and the rest of Zn was 16.8% after 1 h and
6.1% after 0.5 h, respectively. It is obvious that hotter water
results in faster oxidation of Zn to efficiently produce hydrogen
for the conversion of HMF. In addition, XRD patterns in Figure
4 agree with these results. It can be seen that the oxidation of
Zn to ZnO is very quick at 250 oC; peaks of ZnO can be
observed after 10 min. The peaks of ZnO increase with the
time increased from 10 to 30 min, and the peaks of Zn
decrease and vanish at the end.
HTW, as we know, possesses good acid/base catalytic
abilities, and the concentration of H+ and OH- which can be
determined by Kw value is an important factor for acid and
base catalytic performance. Table SI-5 shows the theoretical
values of pKw under different temperatures24. The highest
pKw is 11.2 when the temperature is at 250 oC. Therefore,
HTW at 250 oC was desirable for acid/base catalysed HMF
conversion.
Table 1 and Figure 5 show some results in which the
reactions of formed intermediates were investigated. As
shown in Figure 2, the yield of HDN decreased slowly after 140
min while the yield of 3-MCO kept increasing during the
reaction, suggesting that HDN can be slowly converted to 3-
MCO. As evident from Table 1, 20.9% of HDN was converted to
give 3-MCO in 10.1% yield (entry 1). But the base supplied by
HTW could not catalyze the conversion of HDN into 3-MCO
without any additives (entry 2). When ZnO was added, the
base catalyzed aldol condensation happened (entry 3).
However, the conversion of HDN and the yield of 3-MCO were
low. The previous results, shown in Figure 2, indicated that 3-
MCO production was quick at the beginning of the reaction.
Therefore, it is possible that 3-MCO was generated not only
from HDN, but also from other intermediates. The yield of MF
increased at first and then gradually decreased, suggesting
that MF might be an intermediate (Figure 2). The reaction of
MF gave HDN in 60.2% and 3-MCO in 7.1% yield, respectively,
Figure 4. XRD patterns for the oxidation of Zn into ZnO in
water (25 mmol Zn, 7.5 mL H2O, 250 oC)
4 | J. Name., 2012, 00, 1-3
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Table 1. The investigation of possible intermediates conversion.a
Yield (%)
3-MCO
10.1
0
Feedstoc
Entry
Conv (%)
k
HDN
-
MF
0
0
0
-
MFM
DMF
MCPE
1
HDN
HDN
HDN
MF
20.9
17.2
23.2
100
100
100
100
0.5
0
0
0
0
0
-
0
0
0
0
0
0
-
0
0
0
0
0
0
0
0
2b
3c
4
-
-
6.4
60.2
21.2
25.9
8.9
0
7.1
5d
6d
7
MF
1.3
-
MFM
DMF
3-MCO
19.6
2.6
0
0
0
0
8
-
0
0
aReaction condition: Feedstock (0.17 mmol HDN, 0.19 mmol DMF, 0.20 mmol MF, 0.20 mmol MFM, 0.20 mmol 3-MCO), 25
mmol Zn, 7.5 mL H2O, 250 oC, 140 min; b no Zn was added; c 25 mmol ZnO was added; d The reaction time was 10 min.
23
possible intermediate according to previous report
,
however, when it was used as starting material, the yields of
target products HDN and 3-MCO were very low (entry 7).
However, no DMF was detected in HMF conversion. Therefore,
DMF was not an intermediate in the process. The experiment
of 3-MCO conversion indicated that 3-MCO did not undergo
further conversion under the reaction conditions (entry 8).
Based on the above finding and discussion5,
16,
45-48, the
possible reaction pathways of HMF conversion are illustrated
in Scheme 2. HMF is first converted into MF and then to MFM
by the reaction of in-situ hydrogen generated by oxidation of
Zn in water. Under HTW condition, acid-catalyzed formation of
HDN from MFM is as follows: (1) rehydration of MFM,
followed by (2) a ring opening, and (3) a subsequent
Figure 5. GC-MS chromatogram of main products after the conversion of in-situ produced C=C bond to HND with in-situ
formed hydrogen. Meanwhile, acid-catalyzed rearrangement
to transform MFM into 3-MCO takes place, which involves the
HMF conversion (0.20 mmol HMF, 25 mmol Zn, 7.5 mL H2O,
250 oC)
formation of a carbocation driven by a protonation-
dehydration sequence of the 2-furylcarbinol, and then
at 140 min with 100% conversion of MF, while lower yields
were obtained after the first 10 min (entries 4 and 5). The
conversion of MFM as a starting material gave the yield of
25.9% for HDN and 19.6% for 3-MCO (entry 6). The interesting
thing is that MF was converted completely after 140 min, but
in the previous HMF conversion MF could still be detected
after 480 min (Figure 2). This might be due to the fact that the
in-situ hydrogen first reacted with HMF to produce MF and
then quickly desorbed on the surface of ZnO. After 40 min, Zn
had been almost exhausted and the amount of Zn remained
was only 6.1 wt% at 30 min as mentioned in Figure 3. Thus not
enough in-situ hydrogen was generated to convert MF.
H2O
O
HO
OH
O
O
H
O
H
HO
HO
5
4
OH
O
HMF
acid-catalyzed rearrangement
+ H+
- H2O
in-situ H2
O
O
OH
- H+
H2
in-situ H2
O
O
OH
OH
OH
7
O
OH
6
MF
MFM
O
O
+ H+
+ H2
O
- H2
O
H2
H
3-MCO
MCPE
HO
O
HO
H+
1
aldol condensation
- H+
The change of gas chromatogram during the reaction was
shown in Figure SI-7. Peak 7, MFM, appeared after 10 min and
almost disappeared after 20 min. According to its structure
and previous research 45, MFM might be an important
intermediate for 3-MCO production. Other peaks such as 9, 11,
12 also looked like intermediates, but their structure could not
be confirmed by GC-MS. 2,5-Dimethylfuran (DMF) was also a
- H2O
acid-catalyzed ring opening
O
+ H2
HO
O
O
HO
HDN
2
3
O
Scheme 2. The proposed pathways for the conversion of HMF.
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attack of water as a nucleophile leads to intermediate
undergoes ring opening. 1,4-Dihydroxypentadienyl cation
gives compound through a 4p-conrotatory cyclization. The 11
hydrogenation-dehydration of compound produces 3-MCO.
4
which 10
J. B. Hendrickson and P. S. Palumbo, J. Org. Chem.,
1985, 50, 2110-2112.
5
6
P. Ceccherelli, M. Curini, M. C. Marcotullio, O. Rosati
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W. Kirmse, Angew. Chem. Int. Ed. Engl., 1997, 36, 1164-
1170.
6
Hydrogenation of 3-MCO produces MCPE. Finally, aldol 12
condensation of HDN catalyzed by ZnO gradually occurred to
give 3-MCO.
13
14
15
16
M. L. Karpinski, D. Nicholas and J. C. Gilbert, Org. Prep.
Proced. Int., 1995, 27, 569-570.
E. R. Sacia, M. H. Deaner, Y. L. Louie and A. T. Bell,
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Chem. Int. Ed., 2010, 49, 6616-6618.
In summary, we first developed an efficient method for direct
production of 3-MCO and HDN from bio-based HMF by water
splitting with Zn. In-situ generated hydrogen by oxidation of Zn
in water was effective for the conversion of HMF. The results
indicated that HTW showed good catalytic performance while
the addition of catalysts did not improve the selectivity and
yield in the process. The highest yield of 3-MCO was 30.5% and
F. Liu, M. Audemar, K. De Oliveira Vigier, J. M. Clacens,
F. De Campo and F. Jerome, ChemSusChem, 2014, 7,
2089-2093.
17
18
19
Z. Xu, P. Yan, W. Xu, X. Liu, Z. Xia, B. Chung, S. Jia and Z.
C. Zhang, ACS Catal., 2015, , 788-792.
5
o
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Acknowledgements
The authors gratefully acknowledge the financial support from
The State Key Program of National Natural Science Foundation
of China (No. 21436007). Key Basic Research Projects of
Science and Technology Commission of Shanghai
(14JC1403100). The Program for Professor of Special
Appointment (Eastern Scholar) at Shanghai Institutions of
Higher Learning (ZXDF160002). The Project-sponsored by SRF
for ROCS, SEM (BG1600002). We thank the all reviewers and
editors for reviewing the manuscript and providing valuable
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Production of 2,5-hexanedione and 3-methyl-2-cyclopenten-1-one
from 5-hydroxymethylfurfural
Dezhang Ren, Zhiyuan Song, Lu Li, Yunjie Liu, Fangming Jin and Zhibao Huo*
Graphic abstract