Formation of five-membered carbocycles from D-glucose: A Concise Synthesis of 4-Hydroxy-2-(hydroxymethyl)cyclopentenone

Article abstract of DOI:10.1246/bcsj.20190063

A concise synthesis of 4-hydroxy-2-(hydroxymethyl)cyclo-pentenone (1) has been accomplished from D-glucose by a three-step sequence that features a catalyst-free hydrothermal reaction of D-glucal, which is readily obtained from D-glucose. Optimization of the reaction conditions for synthesizing 1 was performed by changing the temperature and reaction time. The treatment of D-glucal under the optimal conditions, i.e., at 120 °C for 24 h, provided 1 in the highest isolated yield of 61%. 1 would become a versatile intermediate for the synthesis of various fine chemicals having a cyclopentenone structure from cellulosic biomass.

Full text of DOI:10.1246/bcsj.20190063

Document type: Article
Formation of Five-Membered Carbocycles from D-Glucose:
A Concise Synthesis of 4-Hydroxy-2-(hydroxymethyl)cyclopentenone
Yoshitaka Koseki,1,# Toshihiro Watanabe,1,# Takaaki Kamishima,1,2
Eunsang Kwon,3 and Hitoshi Kasai*1
1Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,
2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577, Japan
2FromSeeds Corporation, 6-6-40 Aramaki, Aoba-ku, Sendai, Miyagi 980-0845, Japan
3Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University,
6-3 Aramaki Aza-Aoba, Aoba-ku, Sendai, Miyagi 980-8578, Japan
E-mail: kasai@tohoku.ac.jp
Received: March 9, 2019; Accepted: May 14, 2019; Web Released: June 4, 2019
Hitoshi Kasai
Hitoshi Kasai, is a Professor at the Institute of Multidisciplinary Research for Advanced Materials, Tohoku
University. He received his Ph.D. from Tohoku University in 1996. He was promoted to Associate Professor
in 2004. He joined Precursory Research for Embryonic Science and Technology (PRESTO) in 2007–2011.
He was promoted to Professor in 2016.
Abstract
these research efforts focused on the direct conversion of D-
glucose, whereas our group has investigated the transformation
of deoxy sugars that can be synthesized from D-glucose into
valuable compounds.
Very recently, we reported the synthesis of 4-hydroxy-2-
(hydroxymethyl)cyclopentenone (1). This disubstituted cyclo-
pentenone can be obtained by hydrothermal reaction from 2-
deoxy-D-glucose (2-DG), which is one of the most readily
available industrial deoxy sugars.11 Furthermore, the synthesis
of prostaglandin E1 methyl ester was achieved in six steps from
1. Thus, we consider that 1 is a potential key synthetic inter-
mediate not only for prostaglandins but also for a range of other
bioactive compounds.
A concise synthesis of 4-hydroxy-2-(hydroxymethyl)cyclo-
pentenone (1) has been accomplished from D-glucose by a
three-step sequence that features a catalyst-free hydrothermal
reaction of D-glucal, which is readily obtained from D-glucose.
Optimization of the reaction conditions for synthesizing 1 was
performed by changing the temperature and reaction time. The
treatment of D-glucal under the optimal conditions, i.e., at
120 °C for 24 h, provided 1 in the highest isolated yield of 61%.
1 would become a versatile intermediate for the synthesis of
various fine chemicals having a cyclopentenone structure from
cellulosic biomass.
Keywords: Glucose conversion
j
Hydrothermal reaction
j
Many kinds of five-membered carbocyclic natural products
have been discovered, including litseaverticillols, parthenin, and
pentenomycins. These compounds have been previously syn-
thesized via analogs of 1 as key intermediates (Figure 1).12,13
However, analogs of 1 are currently synthesized from com-
pounds derived from petroleum resources.13 Therefore, the
development of an efficient synthesis method for 1 from plant
biomass resources would contribute to the industrial production
of fine chemicals from non-petroleum resources using 1 as a
feedstock.
Accordingly, in the present study, we developed a method
for efficient synthesis of 1 from D-glucose®one of the most
abundant biomass resources on Earth. We present a concise
synthesis of 1 from D-glucose via a three-step reaction that
involves the quantitative conversion of D-glucose into D-glucal
Biomass feedstock
1. Introduction
Cellulose is the main component of plant biomass resources
and is therefore the most important consideration in the devel-
opment of synthetic methods that convert biomass-derived
feedstocks into valuable fine chemicals.1-4 Cellulose is a poly-
meric compound composed of D-glucose units linked by ¢-1,4-
glycosidic bonds. Accordingly, the hydrolysis of cellulose into
D-glucose by homogeneous,5 heterogeneous,6 and enzymatic
methods7 has been intensively investigated as a means to
produce D-glucose and its derivatives, including bioethanol,8
sorbitol,9 and 5-hydroxymethyl furfural (5-HMF).10 However,
1324 | Bull. Chem. Soc. Jpn. 2019, 92, 1324–1328 | doi:10.1246/bcsj.20190063
© 2019 The Chemical Society of Japan

Instruments. Nuclear magnetic resonance (NMR) spectra
were recorded on a Bruker AVANCE-400 spectrometer. High-
resolution mass spectrometry (HR-MS) was performed with
a Bruker micrOTOF-Q II-S1 by electrospray ionization time
of flight (ESI-TOF) reflectron experiment. Fourier Transform
Infrared (FT-IR) spectra were performed by FT-IR-4200 (Jasco
Corp.). Pellet samples for FT-IR were fabricated using KBr.
Organic
synthesis
OH
O
HO
HO
O
HO
HO
OH
OH
OH
D
-glucal (2)
D
-Glucose
General Organic Synthesis Methods.
Reactions were
Hydrothermal
reaction
monitored by analytical TLC performed on 0.25-mm silica gel
plates. Visualization of the developed plates was performed
using UV absorbance at 254 nm and p-anisaldehyde solution.
Flash chromatography was performed using silica gel with the
indicated solvent systems. NMR spectra were calibrated using
the residual undeuterated solvent as an internal reference
O
OH
HO
4-hydroxy-2-(hydroxymethyl)cyclopentenone (1)
1
(CDCl3 at 7.26 ppm for H and at 77.16 ppm for 13C NMR;
1
CD3OD at 3.31 ppm for H and at 49.00 ppm for 13C NMR;
1
acetone-d6 at δ 2.05 ppm for H and at δ 29.8 and 206.3 for
13C NMR). The following abbreviations are used to explain
NMR peak multiplicities: s = singlet, d = doublet, t = triplet,
m = multiplet, br = broad.
HO
O
O
O
Tri-O-acetyl-D-glucal (2).14,15
To a suspension of D-
R
R1
O
glucose monohydrate (2.00 g, 11.1 mmol) in Ac2O (6.3 mL,
66.6 mmol) was added HBr in AcOH (ca. 5.1 M, 3.2 mL, 16.1
mmol) at room temperature. The reaction mixture was main-
tained for 2.5 h with vigorous stirring, during which time the
suspended solid went into solution. This solution was then
treated with additional HBr in AcOH (ca. 5.1 M, 9.0 mL, 46.0
mmol), and the resulting solution was stirred at room temper-
ature for 16 h. Anhydrous NaOAc (3.6 g, 43.9 mmol) was then
added to neutralize the excess HBr, and this mixture was added
to a suspension of zinc power (11.6 g, 177 mmol), CuSO4¢5H2O
(0.799 g, 3.20 mmol), and anhydrous NaOAc (1.98 g, 23.0
mmol) in a mixture of water (10 mL) and AcOH (15 mL). The
resultant reaction mixture was stirred vigorously at room
temperature for 3 h. The solid was then removed by filtration
and washed first with EtOAc and then with water. The organic
layer of the filtrate was washed with saturated aqueous NaHCO3
and brine and then dried (anhydrous Na2SO4). The solvent was
removed under reduced pressure to provide tri-O-acetyl-D-
glucal (2) (3.00 g, 11.0 mmol, 99%) as a colorless oil. 1H NMR
(400 MHz, CDCl3) ¤ = 2.05 (3H, s), 2.08 (3H, s), 2.10 (3H, s),
4.20 (1H, dd, J = 12.0, 3.2 Hz), 4.24-4.28 (1H, m), 4.40 (1H,
dd, J = 12.0, 8.0 Hz), 4.85 (1H, dd, J = 6.0, 3.2 Hz), 5.23 (1H,
dd, J = 7.6, 5.6 Hz), 5.33-5.36 (1H, m), 6.47 (1H, dd, J = 6.0,
1.2 Hz) ppm. 13C NMR (100 MHz, CDCl3) ¤ = 20.8, 20.9, 21.1,
61.4, 67.2, 67.5, 74.0, 99.0, 145.7, 169.7, 170.5, 170.7 ppm.
D-Glucal (3).16-20 To a solution of tri-O-acetyl-D-glucal
(1.1 g, 4.00 mmol) in MeOH (20 mL) was added NaOMe (10.8
mg, 0.2 mmol), and the mixture was stirred at room temperature
for 5 h. The solution was then neutralized with 1.25 M HCl in
MeOH and the solvent was concentrated under reduced pres-
sure. The residue was purified using silica gel column chro-
matography with EtOAc to obtain D-glucal (3) (0.573 g, 3.92
HO
R2
OH
O
Prostaglangins
Litseaverticillols
Parthenin
O
O
O
OR1
OH
OR2
O
HO
Minwanenone
Pentenomycins
Figure 1. Synthesis of 4-hydroxy-2-(hydroxymethyl)cyclo-
pentenone (1) from D-glucose and representative natural
products containing the cyclopentenone structure.
and subsequent construction of the cyclopentenone structure
via a catalyst-free hydrothermal reaction.
2. Experimental
Materials. D-Glucose, acetic anhydride (Ac2O), copper(II)
sulfate pentahydrate (CuSO4¢5H2O), sodium hydrogen car-
bonate (NaHCO3), and acetic acid (AcOH) were purchased from
FUJIFILM Wako Pure Chemical Corporation. Sodium acetate
(NaOAc), zinc powder, anhydrous magnesium sulfate (MgSO4),
anhydrous sodium sulfate (Na2SO4), methanol (MeOH), and
ethyl acetate (EtOAc) were purchased from Nacalai Tesque, Inc.
Hydrogen bromide (30% in AcOH, ca. 5.1 M) and sodium
methoxide (NaOMe) were purchased from Tokyo Chemical
Industry Co. Hydrogen chloride (HCl, 1.25 M in MeOH) was
purchased from Sigma-Aldrich Co. Chloroform-d (CDCl3) and
acetone-d6 were purchased from Acros Organics and Kanto
Chemical Co., respectively. SEPABEADSTM SP207 was pur-
chased from Mitsubishi Chemical Corporation. Silica gel 60
F254 for thin-layer chromatography (TLC) was purchased from
Merck Millipore. Silica gel 60 N (230-400 mesh) for flash
chromatography was purchased from Kanto Chemical Co., Inc.
All reagents were used without further purification. Sealed
reactor (40 mL) was purchased from ACRAFT.
1
mmol, 98%) as a white solid. H NMR (400 MHz, DMSO-d6)
¤ = 3.57 (1H, dd, J = 9.6, 7.2 Hz), 3.70-3.74 (1H, m), 3.79
(1H, dd, J = 12.0, 5.6 Hz), 3.88 (1H, dd, J = 12.0, 1.2 Hz),
4.12 (1H, ddd, J = 6.8, 2.0, 2.0 Hz), 4.68 (1H, dd, J = 6.4, 2.0
Hz), 6.35 (1H, dd, J = 6.0, 1.6 Hz) ppm. 13C NMR (100 MHz,
CD3OD) ¤ = 62.2, 70.5, 70.8, 80.3, 104.5, 144.9 ppm.
Bull. Chem. Soc. Jpn. 2019, 92, 1324–1328 | doi:10.1246/bcsj.20190063
© 2019 The Chemical Society of Japan | 1325

4-Hydroxy-2-(hydroxymethyl)cyclopentenone (1).11 The
crude D-glucal (3) (ca. 4.00 mmol) in distilled water (20 mL)
was poured into a sealed reactor. The reactor was placed in
a preheated dry oven at 100-160 °C and allowed to stand
without stirring for 1-72 h. After the period of time indicated,
the reactor was removed from the oven and cooled in water
to terminate the reaction. The reaction mixture was filtered,
and the filtrate was applied to a column of SEPABEADSTM
SP207 (15 g) to remove coloring components. The product was
eluted with water (500 mL), which was then removed under
reduced pressure, and the residue was purified using silica gel
column chromatography (EtOAc/MeOH = 20:1) to obtain 1,
deprotection of the acetyl group of 2 using NaOMe/MeOH
affords 3 in 98% yield.
Table 1 shows the conditions for the conversion of 3 into 1.
In the hydrothermal treatments, the concentration of 3 was
fixed at 0.2 M and the reaction conditions were optimized by
changing the temperature and reaction time. An aqueous solu-
tion of 3 was loaded into a sealed reactor and placed in a
constant-temperature drying oven at a reaction temperature in
the range 100-160 °C. After the reaction, the reactor was rap-
idly cooled in an ice-water bath and the reaction mixture was
filtered to remove any insoluble solids. The filtrate was loaded
onto a resin column and eluted with water several times until
it became colorless. After removal of water and purification of
the residue by silica gel chromatography, cyclopentenone 1
was afforded with its isomer 4. 1 and 4 were not separable,
however, the isomerization of 4 to 1 was achieved using acti-
vated alumina to afford a single isomer. After hydrothermal
reaction, the solid which was not soluble in general organic
solvents was obtained as byproduct. The FT-IR spectrum of the
insoluble solid showed the existence of carbonyl and hydroxy
groups similar to that of 1 (Figure S1). Thus, the insoluble
solid was predicted as the polymerized compounds of 1 or 4.
At the lower temperatures of 100 and 120 °C (Entries 1-13), a
long reaction time was required to maximize the yield of 1.
At the condition of 100 °C for 72 h (Entry 7), Formation of
insoluble solid (22 mg) was observed and consequently we
assessed that it would be difficult to improve the yield with
reaction times longer than 72 h at 100 °C. At the higher tem-
peratures of 140 and 160 °C (Entries 14-24), the maximal yield
was achieved in a relatively short time, though the decom-
position of products proceeded faster than at low temperatures.
Overall, the reaction at 120 °C for 24 h (Entry 12) afforded 1 in
the highest isolated yield of 61%. Hence, 1 was synthesized in
59% yield over three steps from D-glucose while the total yield
of 1 in the previous report was 36% over five steps.11,21 In
addition, even if the reaction volume was 10 fold greater, 1 was
obtained in 55% yield at the optimized reaction condition (See
Supporting Information).
1
4, and 5 as a colorless oil. 1: H NMR (400 MHz, acetone-d6):
¤ 2.18 (1H, dd, J = 18.4, 2.0 Hz), 2.72 (1H, dd, J = 18.4,
6.0 Hz), 4.07 (1H, t, J = 5.6 Hz), 4.21-4.23 (2H, m), 4.46 (1H,
d, J = 6.0 Hz), 4.90-4.94 (1H, m), 7.36-7.37 (1H, m) ppm.
13C NMR (100 MHz, acetone-d6): δ 46.0, 56.9, 68.7, 147.7,
157.7, 205.4 ppm. HR-MS (ESI-TOF): m/z calcd. for C6H9O3
([M + H]+), 129.0546, found 129.0552. 5: 1H NMR (400
MHz, CDCl3): ¤ 2.07 (1H, brs), 2.53 (1H, brs), 3.88-3.90
(2H, m), 4.82 (1H, t, J = 5.6 Hz), 6.33-6.34 (1H, m), 6.36
(1H, dd, J = 6.4, 1.6 Hz), 7.40 (1H, dd, J = 1.6, 0.8 Hz) ppm.
13C NMR (100 MHz, CDCl3): ¤ 65.1, 68.4, 107.1, 110.4, 142.4,
153.6 ppm.
Isomerization Reaction 4 into 1. To the mixture of 1 and 4
was added the same amount of activated basic alumina and 10
w/v % of distilled water was added to the mixture and stirred
at 50 °C for 5 h. The resultant mixture was diluted with 2-
propanol (25 mL © 4) and filtered (filter paper, 0.4 ¯m) to
remove the alumina. The solvent was removed under reduced
pressure to provide 1 as a single isomer in quantitative yield.
Conversion to 1 and 4 from 5. A solution of furan 5
(363 mg, 2.83 mmol) in distilled water (14 mL) was poured into
a sealed reactor. The reactor was placed in a preheated dry oven
at 120 °C and allowed to stand without stirring for 12 h. After
the reaction, the same purification procedure for synthesis of 1
was performed to provide a mixture of 1 and 4 (152 mg, 1.19
mmol, 42%) as colorless oil.
The ratio of cyclopentenone 1 and its isomer 4 was deter-
mined by H NMR. A significant difference was observed in
3. Results and Discussion
1
As shown in Scheme 1, our synthesis of 1 begins with the
transformation of D-glucose into tri-O-acetyl-D-glucal (2) and
removal of the acetyl group of 2 to obtain D-glucal (3) accord-
ing to the literature.14-20 Briefly, D-glucose was converted into
2 with 99% yield by a one-pot, three-step procedure that
involved acetylation with acetic anhydride in HBr/AcOH
followed by transformation of the anomeric acetates to the
corresponding bromides with additional HBr/AcOH and finally
reductive elimination of the 1-bromo and 2-acetoxy groups with
Zn/CuSO4¢5H2O in AcOH/water containing NaOAc. Then,
the ratio depending on the reaction time. For shorter reaction
times, the 1/4 ratio was very similar. Conversely, for longer
reaction times, the amount of 1 produced was significantly
higher. This result indicates that an equilibrium between 1 and
4 in the presence of water is established with time, and that
the thermodynamically more stable 1 can be preferentially
obtained by extending the reaction duration. In fact, according
to DFT calculations, 1 showed higher thermodynamic stability
than 4 (Figure S6). When the reaction was stopped before the
formation of the cyclopentenone was completed, furan 5 was
iii) Ac2O, HBr
iii) NaOAc
iii) Zn, CuSO4·5H2O
O
O
OH
AcO
AcO
HO
NaOMe
O
HO
HO
OH
HO
AcOH, H2O
99%
MeOH
98%
OH
OAc
OH
Tri-O-acetyl-
D
-glucal (2)
D-Glucal (3)
D
-Glucose
Scheme 1. Synthesis of D-glucal (3).
1326 | Bull. Chem. Soc. Jpn. 2019, 92, 1324–1328 | doi:10.1246/bcsj.20190063
© 2019 The Chemical Society of Japan

Table 1. Effect of the reaction temperature and reaction time on the yields of 1.
O
O
O
OH
Conditions(a)
H2O
HO
HO
O
OH
OH
OH
+
+
HO
OH
OH
3
1
4
5
Entry
Temp. (°C)
100
Time (h)
Solid (mg)
Yield (%)(b)
Ratio (1/4)(c)
5 (%)(d)
1
2
3
4
5
6
7
1
3
7
5
n.d.
n.d.
n.d.
16
-
1
-
7
7
0
-
21
24
17
14
2
12
24
48
72
6
1 : 2.16
1 : 0.88
1 : 0.15
1 : 0.11
1
32
2
31
22
50
8
9
120
1
3
3
1
n.d.
n.d.
24
-
15
11
20
6
-
10
11
12
13
7
4
1 : 0.87
1 : 0.57
1 : 0.17
1 : 0.04
12
24
48
22
23
95
52
61
1
41
0.3
14
15
16
17
18
140
160
1
3
3
0
n.d.
42
55
55
47
-
3
7
1
1
0
1 : 1.20
1 : 0.41
1 : 0.12
1 : 0.06
7
35
37
66
12
24
19
20
21
22
23
24
1
3
3
20
n.d.
30
47
54
43
21
-
11
14
1
1 : 0.19
1 : 0.10
1 : 0.04
1 : 0.06
1 : 0.06
5
63
7
74
0
12
24
145
199
0
0
(a) Unless stated otherwise, reactions were performed as follows: An aqueous solution of D-Glucal (3)
(4.0 mmol) in H2O (20 mL, 0.2 M) at indicated temperature and for indicated time without stirring.
(b) Isolated yield of 1 including 4. (c) Ratio of 1 and 4 was determined by 1H NMR analysis.
(d) Isolated yield of 5. n.d. = not detected.
found to be present in significant amounts. The conversion of
2-DG affords α,β-unsaturated aldehyde. When the aldehyde
forms Z-isomer, cyclization occurs and following dehydration
of the cyclized product affords the intermediate furan 5. After
that, the furan ring is opened by hydration and cyclized by
intramolecular aldol reaction to form a five-membered carbo-
cycle 4 (pathway A). At the same time, retro reaction also
occurs to form racemic 5 (pathway B). Finally, an equilibrium
reaction occurs between 1 and 4, and then thermodynamically
more stable 1 can be preferentially obtained.
3 into 5 has been reported by treatment of 3 with FeCl3.22
Hydrothermal reaction of isolated 5 at 120 °C for 24 h afforded
1 and 4 in 42% yield. Therefore, we regarded 5 as one of the
intermediates during the conversion of 3 into 1. In addition, the
specific optical rotation of 5 isolated after hydrothermal reac-
23
tion observed racemic {½ꢀꢀD = +0.04 (c = 1.0 in CHCl3)},
whereas the value of 5 prepared by the reaction with FeCl3 was
23
½ꢀꢀD = +32.9 (c = 1.0 in CHCl3); lit.23 [α]D = +36.0 (c = 1.0
in CHCl3).
4. Conclusion
Given these experimental facts, we constructed a reaction
mechanism of the synthesis of 1 (Figure 2). Firstly, 2-DG is
formed by a hydration reaction of 3, and then dehydration of
A new concise synthesis of 4-hydroxy-2-(hydroxymethyl)-
cyclopentenone (1) was achieved from D-glucose through a
Bull. Chem. Soc. Jpn. 2019, 92, 1324–1328 | doi:10.1246/bcsj.20190063
© 2019 The Chemical Society of Japan | 1327

Figure 2. Proposed reaction mechanism of the synthesis of 1.
2010, 12, 1493.
three-step conversion in 59% overall yield. For the hydro-
thermal reaction of D-glucal (3) to 1, the key reaction, reaction
conditions in the temperature range 100-160 °C and the reac-
tion time range 1-72 h were assessed in order to optimize the
yield. The reaction at a temperature of 120 °C for 24 h afforded
1 from D-glucal in the highest isolated yield of 61% in the
present study. The main advantage of the present study is that
we succeeded in the short-step synthesis of five-membered
carbocyclic compound from D-glucose instead of the common
biomass-derived furans such as sorbitol or 5-HMF, etc. We
believe that 1 would become a versatile intermediate for the
production of various fine chemicals using cellulosic biomass
as a feedstock. The synthesis of different cyclopentenones from
1 is now in progress in our group to realize the production of
fine chemicals based on non-petroleum resources.
3
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We would like to thank Prof. Shigefumi Kuwahara and Dr.
Masaru Enomoto of Tohoku University for their help with
measurements of the specific optical rotation. We also thank
Prof. Masaya Mitsuishi and Mr. Hiroaki Ohara for their help
with FT-IR measurements. In addition, we would like to thank
Dr. Toshiyuki Nonaka of FromSeeds Co., Dr. Shigenobu
Aoyagi of Ouchi Shinko Chemical Industrial Co., Ltd., and
Prof. Masaru Watanabe of Tohoku University for productive
discussions. This study was financially supported by the Shorai
Fundation for Science and Technology, the Cooperative
Research Program “Network Joint Research Center for Materi-
als and Devices” and the Research Program “Dynamic Alliance
for Open Innovation Bridging Human, Environment and
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1328 | Bull. Chem. Soc. Jpn. 2019, 92, 1324–1328 | doi:10.1246/bcsj.20190063
© 2019 The Chemical Society of Japan