Practical aqueous reactions leading to skeletally diverse carbohydrate-derived ketones

Article abstract of DOI:10.1039/c4ra14457k

Four types of skeletally diverse compounds have been synthesized from protected aldosyl hemiacetals and methyl ketones using cheap catalysts in water in one pot. Among the four skeletons, two of them are not accessible by current methods. The reactions are operationally simple, high yielding and scalable, which opens a practical channel for utilizing carbohydrates to produce chemical and pharmaceutical intermediates and products.

Full text of DOI:10.1039/c4ra14457k

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Practical aqueous reactions leading to skeletally
diverse carbohydrate-derived ketones†
Cite this: RSC Adv., 2015, 5, 11831
Hongming Liu, Xiaoxing Liu, Lei Liu, Xixi Zhang and Chunbao Li*
Four types of skeletally diverse compounds have been synthesized from protected aldosyl hemiacetals and
methyl ketones using cheap catalysts in water in one pot. Among the four skeletons, two of them are not
accessible by current methods. The reactions are operationally simple, high yielding and scalable, which
Received 13th November 2014
Accepted 12th January 2015
DOI: 10.1039/c4ra14457k
opens
a practical channel for utilizing carbohydrates to produce chemical and pharmaceutical
www.rsc.org/advances
intermediates and products.
acetophenone catalyzed by 2.0 equiv. of LiOH mediated by
water. In that work, the 1,5-pentanedione product was isolated
Introduction
5
Carbohydrates are annually renewable and the quantities and puried aer TLC indicated that the aldol reaction was
produced exceed those for other renewable organic compounds. complete. In this work, aer the completion of the aldol reac-
Therefore utilizing carbohydrates for chemical, energy and tion, the reaction mixture was treated with 2.5 equiv. of 10%
material supplies to replace fossil fuels is an important area for HCl, in which 2.0 equiv. of HCl was used to neutralize the 2.0
1
sustainable development. Partially modied carbohydrates are equiv. of LiOH and the remaining 0.5 equiv. of HCl was used to
important drugs, such as iminosugars which are used to treat catalyze the hydrolysis of the enolether. The reaction was then
1f,2
ꢀ
diabetes. When carbohydrates are dehydrated and cyclized, continued at 60 C for 8 h, to give furanyl-substituted diketone
they form hydroxymethyl furfural, which is a potential green Ia (Scheme 1) in 83% yield aer in-ask extraction and ltration
3
fuel, and can then be transformed into a series of chemicals. In through a silica gel pad.
the synthesis of natural products and other chemicals, carbo-
hydrates are oen transformed into basic building blocks.
To test the scope of the reaction, a series of substituted
acetophenones were used for the condensation reactions with
1c,d,4
In these processes, expensive reagents, harsh reaction condi- O-benzyl-protected D-glucosyl and D-xylosyl hemiacetals, fol-
tions, prolonged reaction times or organic solvents are oen lowed by one-pot hydrolysis. Using different substituents on the
required, which make the manufacture of these carbohydrate- phenyl rings had little impact on the reaction yields and rates
derived products impractical due to high costs and adverse (Scheme 1, 1a–1g) showing that the scope of usable substrates is
2
–4
environmental effects. Therefore, it is benecial to develop wide. The reaction yields varied from 73–87% and the reaction
operationally simple and economical procedures to produce times from 8–32 h.
carbohydrate-derived chemicals using green media and cheap
Subjecting aliphatic ketones and carbohydrates to a similar
catalysts. Herein, the synthesis of dienediketones, ene- reaction led to another type of product, a,b-unsaturated ketones
triketones, furanyl-substituted a,b-unsaturated ketones and (Scheme 1, 2a–e). The reaction yields ranged from 76–95% and
furanyl-substituted diketones from protected carbohydrates the reaction times were 2–20 h. In the synthesis of both 1 and 2,
and methyl ketones using inexpensive catalysts in water is the reaction times for O-benzyl-protected D-glucosyl hemiacetals
reported.
were much longer than those of O-benzyl-protected D-xylosyl
hemiacetals (1g, 32 h and 2b, 20 h; 1a, 8 h and 2a, 2 h). When
more catalyst was used (3.0 equiv. of HCl), the reaction times for
Results and discussion
1g and 2b were shortened from 32 h and 20 h to 3 h and 2 h
respectively. The reactions are easily scalable since similar
yields of both 1a and 2b were produced when the amounts of
aldosyl hemiacetal starting materials were raised from 0.1 g
to 10 g.
Previously, we synthesized (S,Z)-3-(1,3-bis(benzyloxy)-4-hydroxy-
1-butenyl)-1,5-diphenyl-1,5-pentanedione (Scheme 2, Ia) from a
reaction between O-benzyl-protected D-xylosyl hemiacetal and
These furanyl-substituted products are also accessible
staring from furfurals and methyl ketones via aldol reactions.
Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072, P. R.
China. E-mail: lichunbao@tju.edu.cn; Fax: +862227403475; Tel: +86-022-27892351
6
The method reported here provides an alternative to known
†
Electronic supplementary information (ESI) available: General experimental
information, general procedure for all products, spectral data for all products, methods with advantages of using carbohydrates instead of
references for known compounds, NMR spectra of the products, See DOI:
furfurals and using water as the solvent. The better performance
1
0.1039/c4ra14457k
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cyclizing to form furan Va. A bulkier substituent on the g
position of IIIa results in a lesser amount of cis-unsaturated
7
ketone IVa in the equilibrium. Therefore the reactions start-
ing from xylose (Scheme 1, 1a, 2a) were much faster than those
starting from glucose (Scheme 1, 1g, 2b). The aldol reaction
product Ib was transformed into Vb via a pathway that is
similar to that for Ia.
To obtain useful chemical intermediates as well as to prove
the reaction mechanism, the reaction conditions used in
Scheme 1 were modied by treating the aldol condensation
reaction mixture from the acetophenone and O-benzyl-
protected D-xylosyl hemiacetal with less HCl (2.1 equiv.
instead of 2.5 equiv. of Scheme 1). The reaction took 10 min at
ꢀ
6
0 C to produce triketone 3a (Scheme 3) in 86% yield. Further
transformation of 3a into furan 1a was successfully avoided by a
timely workup.
A series of substituted aryl methyl ketones were then reacted
with O-benzyl-protected D-glucosyl and D-xylosyl hemiacetals
under these conditions to produce triketones 3a–3o (Scheme 3).
The substituents on the aromatic ring of the methyl ketones
included electron-withdrawing (F
3
C– on 3e, 3m and F– on 3b,
3g), electron-neutral (H– on 3a, 3i) and electron-donating (BnO–
on 3f, 3o) groups. All the reactions proceeded expeditiously and
gave good to excellent yields. Enetriketone 3a was prepared
starting with 10 g of O-benzyl-protected D-xylosyl hemiacetal
with a similar reaction rate and yield as those obtained with 0.1
g of the hemiacetal.
Several methods to prepare triketones have been reported
in the literature. A four-component radical coupling reaction
of iodide, CO, a,b-unsaturated ketones and tin enolates
9
leading to triketones was reported by Hosomi and Ryu et al.
Stetter and Simons reported that a thiazolium salt-catalyzed
addition of aldehydes to 2-methylene-l,4-ketoketals produces
1
0
triketones. However, the enetriketone skeleton reported here
has not been described in any references. Extending the
known methods to build this type of skeleton would be
expected to be quite difficult in regards to achieving the
desired chemoselectivities and with respect to the availability
of starting materials. Furthermore, the known methods use
Scheme 1 One-pot synthesis of furanyl-substituted diketones 1 and
furanyl-substituted a,b-unsaturated ketones 2 from aldosyl hemi-
a,b
a
acetals and methyl ketones
.
Reaction conditions: (1) aldosyl
hemiacetal (0.25 mmol), methyl ketone (6.0 equiv. for 1a–1h, 3.0
equiv. for 2a–2d), LiOH (2.0 equiv.), TBAB (1.0 equiv.), water (0.5 mL), volatile organic solvents, expensive reagents or high pressures.
ꢀ
6
0 C, 15 min for 1 and 2. (2) 10% HCl aq (2.5 equiv.) 8 h for 1a–1f, 32 h Our one-pot procedure employs water as the reaction media
b
for 1g and 1h, 2 h for 2a, 2c and 2e, 20 h for 2b and 2d. Isolated yields.
b-hydroxyandrost-5-en-17-one (0.25 mmol), aldosyl hemiacetal
2.2 equiv.).
and the phase transfer catalyst (TBAB) and catalyst (HCl) are
cheap and water-soluble. The hydroxyl and benzyloxy func-
tional groups on the enetriketone skeleton are additional
advantages of our approach.
c
3
(
Encouraged by the successful synthesis of 3a–3o (Scheme 3),
we attempted to prepare dienediketone 4a (Scheme 4) via a
similar reaction. However, reacting crude aldol product
of the water-mediated aldol reaction than the organic solvent-
mediated one is attributed to the heteroatom effects. The
5
furan-forming step could be achieved in organic solvents and in
(
4
S,5E,7Z)-7,9-bis(benzyloxy)-10-hydroxy-2-methyl-5,7-decadien-
-one (Scheme 2, Ib) from the reaction between 4-methyl-2-
7
water.
5
A possible pathway for the one-pot reaction is shown in
Scheme 2. First, the acidic hydrolysis of the enolether group of
the aldol product Ia condensed from two methyl ketones and a
carbohydrate to give IIa, which eliminated benzyl alcohol,
pentanone and O-benzyl-protected D-xylosyl hemiacetal with
ꢀ
less HCl (#2.5 equiv.) at temperatures ranging from 0 to 60 C
led to the formation of furan 2a (Scheme 1), and in all cases 4a
was not formed.
So the crude aldol product was subjected to in-ask
extraction and concentration, which was then treated with
8
yielding the trans-unsaturated ketone IIIa. The cis-unsatu-
rated ketone IVa is in equilibrium with the trans isomer IIIa
under the acidic conditions. Only the former is capable of
2 2 4 3 3
different acids (AcOH, ZnCl , H SO , TsOH, AlCl , BF or
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Scheme 2 A possible pathway for the one-pot synthesis of furanyl-substituted diketones and furanyl-substituted a,b-unsaturated ketones.
FeCl
CH Cl
catalyzed by all the acids except FeCl $6H O led to furan 2a as intermediate. The dienediketones synthesized here are an
3
$6H
2
O) in different solvents (DMSO, toluene, CHCl
3
,
the mechanism research for the transformation of hexose to
2
2
, methanol, 1,4-dioxane or EtOAc). The reactions hydroxymethyl furfural, 3,4-deoxyglucosene was proposed to be an
12
3
2
the major product. The reaction catalyzed by FeCl $6H O did advanced skeleton, which are not accessible via extending the
3
2
not occur in DMSO and was sluggish (>10 h) in methanol and known methods.
,4-dioxane. The reaction went to completion in toluene,
CHCl and CH Cl but the products were contaminated with
substantial amounts of furan 2a. The reaction product was
pure only when mediated by ethyl acetate. The amount of General experimental information
1
3
2
2
Experimental
FeCl
.1 to 2.0 equiv. and 1.5 equiv. was found to be optimal. If less
than 1.5 equiv. of FeCl $6H O were used, the reaction was
slow and the side product 2a formed. The better performance
of the ethyl acetate-mediated reaction is probably due to the
chelation of the lone paris of ethyl acetate oxygen atoms
3 2
$6H O was optimized by screening catalyst loads from
All of the chemicals were obtained from commercial sources
or prepared according to standard methods. NMR spectra were
0
3
2
1
recorded with a 600 MHz spectrometer for H NMR, 151 MHz
13
for C NMR using TMS as an internal standard. Chemical
1
13
shis (d) are reported relative to TMS ( H) or CDCl3 ( C).
Multiplicities are reported as follows: singlet (s), doublet (d),
triplet (t), quartet (q), multiplet (m), dd (doublet of doublets)
and dt (doublet of triplets). Coupling constants were reported
in Hertz (Hz). Melting points were recorded with a micro
melting point apparatus. Infrared analyses (KBr pellet) were
performed by FT-IR. High resolution spectra (HRMS) were
recorded on a QTOF mass analyzer with electrospray ioniza-
tion (ESI†).
with FeCl
3
, which does not occur for toluene, CHCl
3
and
CH Cl . The ethyl acetate chelates with FeCl
2
2
3
which prevents
it from further catalyzing reactions that lead to the side
product furan.
Altogether nine dienediketones (Scheme 4, 4a–i) were
obtained in good to excellent yields using these conditions
3 2
(FeCl $6H O catalyst in ethyl acetate). There was a slight
difference in the method used to synthesize the glucose-derived
dienediketones and that for the xylose-derived dienediketones.
For the glucose-derived dienediketones (4b, 4d, 4f, 4i), 1.0
General procedure for the synthesis of furanyl-substituted
diketone 1
equiv. of FeCl
excellent (81–91%). For the xylose-derived dienediketones (4a,
c, 4e, 4g, 4h), the amount of catalyst was increased to 1.5 equiv.
3 2
$6H O was used, and the yields were good to
To a 10 mL test tube were added aldosyl hemiacetal (0.25
mmol), methyl ketone (6 equiv.), LiOH (2 equiv.), TBAB
4
in order to increase the reaction rate. This decreased the
production of the side product furans. These reaction condi-
tions are tolerant to ketone (4a–i), ketal (4c, 4d), olen (4g),
small rings (4e, 4f), hydroxyl (4h, 4i) and ether (4g) groups. In
addition the reaction was scalable and the amount of O-benzyl-
protected D-glucosyl hemiacetal starting material could be
increased from 0.1 g to 10 g for the preparation of 4b with the
same yield and reaction rate.
(
1 equiv.) and water (0.5 mL). The mixture was stirred and
ꢀ
heated at 60 C for 15 min and TLC indicated completion of the

rst step. Then 10% HCl aq. (2.5 equiv.) was added to the test
ꢀ
tube, which was kept at 60 C until TLC indicated completion of
the reaction (1a–f 8 h, 1g, 1h 32 h). The reaction was stopped
and in-tube extracted with ethyl acetate (3 Â 2 mL), dried over
2 4
Na SO and puried on a silica gel pad (eluted with petroleum
ether/ethyl acetate) to give products 1a–1h.
Followings are two relevant research reports in the literature.
On the nonenzymatic generation of oxidized lipids, it was reported
that a six-step procedure starting from 1-hexyne and substituted
The synthesis of 1a starting from 10 g of O-benzyl-protected
D-xylosyl hemiacetal was performed in a 100 mL round-bottom

ask in the same conditions yielding 1a (6.5 g, 86%, t
1
: 0.33 h,
11
furans leads to 2,4-diene-1,4-diketones in less than 30% yield. In
2
t : 9 h).
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Scheme 4 Synthesis of dienediketones from aldosyl hemiacetals and
a
methyl ketones. Reaction conditions: (1) aldosyl hemiacetal (0.5
mmol), methyl ketone (3.0 equiv.) except for (4h, 4i), LiOH (2.0 equiv.),
ꢀ
TBAB (1.0 equiv.), water (1 mL), 60 C, 15 min. (2) FeCl
3
$6H
2
O (1.5
equiv.) for 4a, 4c, 4e, 4g, 4h, (1.0 equiv.) for 4b, 4d, 4f, 4i, ethyl acetate
b
c
(
2 mL), rt. Isolated yields. For 4h and 4i 3b-hydroxyandrost-5-en-17-
one (0.25 mmol), aldosyl hemiacetal (2.2 equiv.).
General procedure for the synthesis of furanyl-substituted
a,b-unsaturated ketones 2
To a 10 mL test tube were added aldosyl hemiacetal (0.25
mmol), methyl ketone (3 equiv.), LiOH (2 equiv.), TBAB (1
equiv.) and water (0.5 mL). The mixture was stirred and heated
ꢀ
at 60 C for 15 min and TLC indicated completion of the rst
step. Then 10% HCl aq. (2.5 equiv.) was added to the test tube,
ꢀ
which was kept at 60 C until TLC indicated completion of the
reaction (2a, 2c 2 h, 2b, 2d 20 h). The reaction was stopped and
in-tube extracted with ethyl acetate (3 Â 2 mL), dried over
Na SO and puried on a silica gel pad (eluted with petroleum
2
4
ether/ethyl acetate) to give products 2a–2d.
The synthesis of 2b starting from 10 g of O-benzyl-protected
D-glucosyl hemiacetal was performed in a 100 mL round-bottom

1
ask in the same conditions yielding 2b (4.63 g, 84%, t : 0.33 h,
t
2
: 22 h).
To a 10 mL test tube were added 3b-hydroxyandrost-5-en-17-
one (0.25 mmol), aldosyl hemiacetal (1.2 equiv.), LiOH (2
equiv.), TBAB (1 equiv.) and water (0.5 mL). The mixture was
acetals and methyl ketones. Reaction conditions: (1) aldosyl hemi- stirred and heated at 60 C for 1.5 h. Then more aldosyl hemi-
Scheme 3 One-pot synthesis of enetriketones from aldosyl hemi-
a
ꢀ
acetal (0.25 mmol), methyl ketone (6.0 equiv.), LiOH (2.0 equiv.), TBAB acetal (1 equiv.) was added. Aer 0.5 h, TLC indicated comple-
ꢀ
(
(
1.0 equiv.), water (0.5 mL), 60 C, 15 min except for 3f (3 h), 3j (1 h), 3n
tion of the rst step. Then 10% HCl aq. (2.5 equiv.) was added
and the reaction was stirred at 60 C until TLC indicated
b
0.5 h), 3o (13 h). (2) 10% HCl aq (2.1 equiv.), 10 min. Isolated yields.
ꢀ
completion of the reaction (2 h). The reaction was stopped and
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in-tube extracted with ethyl acetate (3 Â 2 mL), dried over methyl ketones have been developed. Two of these skeletons are
Na SO and puried on a silica gel pad (eluted with petroleum not accessible via current methods. Inexpensive catalysts were
2
4
ether/ethyl acetate) to give product 2e.
used in all cases and in most cases, aqueous media were used.
The reaction yields were good to excellent and the operations
simple. The four types of ketones have all been scaled up to
using 10 g of carbohydrate starting material. The products
should be useful intermediates for chemical and pharmaceu-
tical industries. In his paper on the principles of utilizing
carbohydrates to produce chemicals, Lichtenthaler et al. stated
that: “Unlike fossil resources, which essentially are devoid of
oxygen, carbohydrates are overfunctionalized with hydroxyl
groups, thus requiring efficient methodologies for the simul-
taneous reduction of their oxygen content and the introduction
General procedure for the synthesis of enetriketone 3
To a 10 mL test tube were added aldosyl hemiacetal (0.25
mmol), methyl ketone (6 equiv.), LiOH (2 equiv.), TBAB (1
equiv.) and water (0.5 mL). The mixture was stirred and heated
ꢀ
at 60 C for 15 min and TLC indicated completion of the rst
step. Then 10% HCl aq. (2.1 equiv.) was added to the test tube,
ꢀ
which was kept at 60 C for 10 min. The reaction was stopped
and in-tube extracted with ethyl acetate (3 Â 2 mL), dried over
2 4
Na SO and puried on a silica gel pad (eluted with petroleum
4a,1
of C]C and C]O unsaturations”.
This work meets these
ether/ethyl acetate) to give products 3a–3o.
The synthesis of 3a starting from 10 g of O-benzyl-protected
D-xylosyl hemiacetal was performed in a 100 mL round-bottom
requirements. Research on transforming these C]O and C]C
containing compounds into other chemicals is currently
underway in our laboratory.

ask in the same conditions yielding 3a (7.04 g, 88%, t : 0.33 h,
1
t2: 0.25 h).
Notes and references
General procedure for the synthesis of dienediketone 4
To a 10 mL test tube were added aldosyl hemiacetal (0.25
mmol), methyl ketone (3 equiv.), LiOH (2 equiv.), TBAB (1
equiv.) and water (0.5 mL). The mixture was heated and stirred
1 (a) F. W. Lichtenthaler, Carbohydr. Res., 1998, 313, 69–89; (b)
N. Kardos and J. Luche, Carbohydr. Res., 2001, 332, 115–131;
(c) S. M. Andersen, I. Lundt, J. Marcussen and S. Yu,
Carbohydr. Res., 2002, 337, 873–890; (d) P. Gallezot, Catal.
Today, 2007, 121, 76–91; (e) P. Gallezot, Green Chem., 2007,
9, 295–302; (f) S. Jarosz, M. Magdycz and B. Lewandowski,
Carbohydr. Chem., 2009, 35, 232–258; (g) J. Dam and
U. Hanefeld, ChemSusChem, 2011, 4, 1017–1034; (h)
J. O. Metzger, ChemCatChem, 2013, 5, 680–682.
ꢀ
at 60 C for 15 min and TLC indicated completion of the reac-
tion. The reaction was in-tube extracted with ethyl acetate (3 Â 2
2 4
mL), dried over Na SO . Aer concentration to about 2 mL,
3 2
FeCl $6H O (1.5 equiv. for 4a, 4c, 4e, 4g, 1.0 equiv. for 4b, 4d, 4f)
was added to the ethyl acetate solution, which was stirred at rt
for a certain period (4a 1.5 h, 4b 3.5 h, 4c 2 h, 4d 5 h, 4e 1.5 h, 4f
4
h, 4g 0.25 h). The reaction was stopped by addition of Na CO3
2 For reviews on iminosugars see: (a) V. H. Lillelund,
H. H. Jensen, X. Liang and M. Bols, Chem. Rev., 2002, 102,
517; (b) M. S. M. Pearson, M. Math ´e -Allainmat, V. Fargeas
and J. Lebreton, Eur. J. Org. Chem., 2005, 2159–2191; (c)
B. G. Winchester, Tetrahedron, 2009, 20, 645–651; (d)
B. L. Stocker, E. M. Dangereld, A. L. Win-Mason,
G. W. Haslett and M. S. M. Timmer, Eur. J. Org. Chem.,
2010, 1615–1637.
2
(5 equiv.) under stirring. Then the solution was ltered and the

ltrate was puried on a silica gel pad (eluted with petroleum
ether/ethyl acetate) to give products 4a–4g.
The synthesis of 4b starting from 10 g of O-benzyl-protected
D-glucosyl hemiacetal was performed in a 100 mL round-bottom

1
ask in the same conditions yielding 4b (5.09 g, 87%, t : 0.33 h,
: 4 h).
t
2
To a 10 mL test tube were added 3b-hydroxyandrost-5-en-17-
3 For reviews on HMF see: (a) A. A. Rosatella, S. P. Simeonov,
R. F. M. Frade and C. A. M. Afonso, Green Chem., 2011, 13,
754–793; (b) R. Putten, J. C. Waal, E. Jong, C. B. Rasrendra,
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F. W. Lichtenthaler, Acc. Chem. Res., 2002, 35, 728–737; (d)
D. Martin and F. W. Lichtenthaler, Tetrahedron, 2006, 17,
756–762.
one (0.25 mmol), aldosyl hemiacetal (1.2 equiv.), LiOH (2
equiv.), TBAB (1 equiv.) and water (0.5 mL). The mixture was
ꢀ
heated and stirred at 60 C for a certain period (4h 1.5 h, 4i 2 h),
then more aldosyl hemiacetal (1 equiv.) was added. Aer 0.5 h,
TLC indicated completion of the reaction, which was in-tube
extracted with ethyl acetate (3 Â 2 mL), dried over Na
Aer concentration to about 2 mL, FeCl $6H O (1.5 equiv. for
h, 1.0 equiv. for 4i) was added to the ethyl acetate solution,
which was stirred at rt for a certain period (4h 2 h, 4i 4 h). The
reaction was stopped by addition of Na CO (5 equiv.) under
2 4
SO .
3
2
4
2
3
5 (a) B. Li and C. Li, J. Org. Chem., 2014, 79, 2242–2254; (b) B. Li
and C. Li, J. Org. Chem., 2014, 79, 8271–8277.
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puried on a silica gel pad (eluted with petroleum ether/ethyl
acetate) to give products 4h and 4i.
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Conclusions
In conclusion, one-pot methods to synthesize four types of
skeletally diverse compounds starting from carbohydrates and
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Paper
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11836 | RSC Adv., 2015, 5, 11831–11836
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