Tin-catalyzed conversion of biomass-derived triose sugar and formaldehyde to α-hydroxy-γ-butyrolactone

Article abstract of DOI:10.1039/c4cc00954a

The direct conversion of biomass-derived 1,3-dihydroxyacetone (DHA) and formaldehyde to α-hydroxy-γ-butyrolactone (HBL) was achieved through the use of tin(IV) chloride and a small amount of water and the yield reached up to 70%. The reaction mechanism was also investigated by incorporating d ₂-formaldehyde into the reaction mixtures. the Partner Organisations 2014.

Full text of DOI:10.1039/c4cc00954a

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Tin-catalyzed conversion of biomass-derived
triose sugar and formaldehyde to
a-hydroxy-c-butyrolactone†
Cite this: Chem. Commun., 2014,
0, 4600
5
Received 5th February 2014,
Accepted 12th March 2014
Sho Yamaguchi, Ken Motokura, Yasuharu Sakamoto, Akimitsu Miyaji and
Toshihide Baba*
DOI: 10.1039/c4cc00954a
www.rsc.org/chemcomm
The direct conversion of biomass-derived 1,3-dihydroxyacetone considerable issue to overcome. In addition, a strict control of
DHA) and formaldehyde to a-hydroxy-c-butyrolactone (HBL) was anticipated competitive reactions, i.e. the retro-aldol reaction and
(
achieved through the use of tin(IV) chloride and a small amount of the isomerization reaction, is required. Thus far, the successful
water and the yield reached up to 70%. The reaction mechanism examples of the aldol reaction of DHA with formaldehyde, developed
was also investigated by incorporating d
reaction mixtures.
2
-formaldehyde into the exclusively for the selective syntheses of unprotected sugars, have been
7
8
carried out under either basic or enzymatic conditions. On the other
hand, Lewis acid catalysts are barely employed for the aldol reaction
a-Hydroxy-g-butyrolactone (HBL) is an important starting material of DHA with formaldehyde although they are known to be especially
in pharmaceutical synthesis. The methods of making HBL itself effective as catalysts for the conversion of DHA to lactic acid deriva-
1
9
which have been reported to date are based on either multi-step tives. Hence, in this work, we focused on Lewis acid catalysts as the
conversions or multi-component reactions, and so there is still a activator for the DHA/formaldehyde coupling reaction producing HBL
demand for a more efficient and economical approach to the and found that tin catalysts have a specific activity to the coupling
synthesis of HBL.
reaction and gave HBL in high yield.
Carbohydrates derived from lignocellulose materials comprise
the largest fraction of terrestrial biomass and various strategies for in the presence of anhydrous SnCl
their efficient use as commercial chemical feedstocks are currently listed in Table 1 entry 1, the desired product 2 was obtained in 40%
The reaction of DHA (1) and formaldehyde was initially examined
2
10
4
in 1,4-dioxane at 140 1C. As
11
12
being established with the aim of supplementing and ultimately yield while lactic acid (3) was generated in 17% yield as a
3
replacing fossil fuels. Herein we describe a novel transformation of by-product. Although the conversion of DHA (1) was extremely high,
a triose sugar and formaldehyde, both of which are generated from we couldn’t identify any co-products other than 3. The subsequent
carbohydrates, into HBL. The triose sugar, 1,3-dihydroxyacetone use of the tin hydrates SnCl
4
–5H
2 2 2
O and SnCl –2H O provided 2 in 48
4
5
(
DHA), is obtained from the stoichiometric or catalytic oxidation and 20% yields, respectively (entries 2 and 3). The combination of
6
4
of glycerol or from the fermentation of sugars and represents an anhydrous SnCl and a small amount of water, however, resulted in
abundant precursor for the production of important materials improved reaction efficiency compared to the results obtained with
involved in the synthesis of several fine chemicals. In addition, SnCl –5H O, and provided 2 in 63% yield, although the yield of 3
4
2
formaldehyde is the simplest possible oxygenated compound was also increased to 20% (entry 4). These results indicate that a
which may be obtained from carbohydrate resources. small amount of water could be an important additive with regard to
Regarding the above coupling reaction, the dimerization the promotion of the aldol reaction. When an excess of DHA (1) was
reaction between DHA molecules as well as the coupling applied, 2 was afforded in 59% yield (entry 5). Increasing the
frequency between DHA and formaldehyde appears to be a concentration of DHA (1) might lead to the polymerization among
the DHA (1) molecules. In contrast, an excess amount of formalde-
hyde afforded 2 in 70% yield (the highest of all yields, entry 6), along
with a dramatic decrease in the yield of 3 compared to the yield seen
in entry 4. When other tin(II) or (IV) catalysts were applied (Sn(OAc)2,
Sn(OTf) and SnO ) with a small amount of water or hydrogen
Department of Environmental Chemistry and Engineering, Interdisciplinary
Graduate School of Science and Engineering, Tokyo Institute of Technology,
4
259-G1-14 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan.
E-mail: tbaba@chemenv.titech.ac.jp; Fax: +81-(0)-45-924-5441;
Tel: +81-(0)-45-924-5480
2
2
chloride, the desired product 2 was not obtained (entries 7–10).
In addition, the Lewis acid catalysts AlCl , TiCl and ZrCl , all of
†
Electronic supplementary information (ESI) available: Detailed experimental
1
procedures, and compound characterization, including H NMR spectra for HBL
2) and d -HBL (4). See DOI: 10.1039/c4cc00954a
3
4
4
9
(
2
which have been reported to activate DHA, were observed to
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Table 1 Transformation of DHA (1) and formaldehyde into HBL (2) using
a
various catalysts
1
2
Fig. 1 H NMR spectra of (a) HBL (2) and (b) d -HBL (4).
Conversion Yield
Yield
c
b
c
c
Entry Catalyst
Additive
of 1 (%)
of 2 (%) of 3 (%)
1
2
3
4
5
6
7
8
9
1
1
1
1
1
SnCl
SnCl
SnCl
SnCl
SnCl
SnCl
4
4
2
4
4
4
—
—
—
499
499
499
499
499
499
499
499
95
499
499
499
499
79
40
48
20
63
59
70
0
0
0
0
0
17
14
8
20
40
5
–5H
–2H
2
O
O
2
H
2
H
2
H
2
H
2
H
2
H
2
O
O
O
O
O
O
d
e
Sn(OAc)
Sn(OTf)
2
5
2
36
Trace
15
5
2
18
4
SnO
SnO
AlCl
TiCl
2
2
3
4
f
0
1
2
3
4
HCl + H
2
O
H
2
H
2
H
2
H
2
O
O
O
O
0
0
0
ZrCl
No catalyst
4
2
Fig. 2 Mass spectra of (a) HBL (2) and (b) d -HBL (4).
a
10
Reaction conditions: 1 (1.25 mmol), paraformaldehyde (1.31 mmol),
1
,4-dioxane (4.0 mL), catalyst (0.171 mmol), Ar, 3 h, 140 1C. Using an
b
internal standard technique. Yields were based on 1. A 1.11 mmol
c
1
2
quantity of H O was used. Yields were determined by H NMR analysis.
In addition, GC-MS analysis confirmed the formation of d -HBL
2
d
Using 1 (3.75 mmol) and paraformaldehyde (1.25 mmol). Yields of 2
+
(
Fig. 2). The m/z [M ] values of HBL (2) and d
2
-HBL (4) were 103
(1) and 105 (1), respectively and the m/z [M À HCO ] of HBL (2)
and d -HBL (4) were 57 (100) and 59 (100). These results
indicate that the deuterium atoms were incorporated adjacent
have no activity in this reaction (entries 11–13). These results to the ether oxygen atom of d -HBL.
indicate that the combination of SnCl with a small amount of A proposed reaction pathway is shown in Scheme 2. This
water is absolutely necessary for the successful progression of transformation involves the following four steps: (a) isomeriza-
this reaction. tion and dehydration of DHA (1) to pyruvic aldehyde (PA) (6), (b)
The transformation of DHA and formaldehyde into HBL was an aldol reaction between 6 and formaldehyde, (c) formation of
confirmed by incorporating d -formaldehyde into the reaction the five-membered ring in 9 and (d) proton transfer to form
mixtures. Scheme 1 shows the reaction between DHA and HBL (2). Transformation of DHA into PA is achieved through the
e
and 3 were based on formaldehyde and 1, respectively. Using 1
+
f
(
(
1.25 mmol) and paraformaldehyde (3.75 mmol). Using 28.5 ml of HCl
37 wt%) containing 1.11 mmol of water.
2
2
2
4
2
9
d
2
-formaldehyde using SnCl
4
and a small amount of water to use of SnCl
4
, as noted in previous reports. Subsequently, PA is
-HBL (4) in 48% yield. Fig. 1 presents the H NMR likely converted to the Sn enolate 7 by SnCl while formaldehyde
spectra of (a) HBL (2) and (b) d -HBL (4), respectively. The peaks is activated by hydrogen chloride evolved simultaneously with the
1
3
1
generate d
2
4
2
14
at 4.42 (*) and 4.21 ppm (K), which represent the two protons formation of 7, such that the aldol reaction proceeds more
next to the ether oxygen atom, are seen to disappear in Fig. 1b. effectively compared to the alternate reaction which generates
lactic acid. Then the effect of the addition of a small amount of
water seems to promote the generation of hydrogen chloride.
Finally, the formation of the 5-membered ring proceeds smoothly,
followed by an intermolecular proton transfer to provide HBL.
Although we attempted to elucidate the structures of the inter-
mediates 6, 8 and 9 to validate this proposed reaction mechanism,
this analysis was not possible since the intermediates were
unstable under these reaction conditions. To strengthen the
Scheme 1 The reaction of DHA (1) and d
SnCl and a small amount of water. Reaction conditions: DHA (1) (1.25 mmol),
-paraformaldehyde (1.31 mmol), SnCl (0.171 mmol), H O (1.11 mmol),
,4-dioxane (4.0 mL), Ar, 3 h, 140 1C, using an internal standard technique.
2
-formaldehyde catalyzed with
proposed reaction pathway, a separate reaction of glyceraldehyde
GA) (5) with formaldehyde was carried out. Based on the optimized
4
(
d
2
4
2
1
0
conditions, the desired product 2 was obtained in 57% yield.
1
Yield was based on 1.
On the other hand, the above coupling reaction without the
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Scheme 2 Proposed pathway to HBL (2) from DHA (1) and formaldehyde.
presence of SnCl
4
catalyst didn’t afford HBL (2) although the
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results also support the proposed reaction pathway as shown
in Scheme 2.
7
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In conclusion, we have achieved the direct transformation of
DHA and formaldehyde into HBL using a homogeneous tin
catalyst in conjunction with a trace of water. Among the Lewis
acid catalysts examined, tin(IV) chloride exhibited the highest
performance and the addition of a small amount of water was
found to be crucial to the success of this reaction system. This
transformation will be applicable to the synthesis of HBL deriva-
tives and should contribute to the future development of various
green and sustainable chemical processes.
8
2
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1
1
11
12
13
1
3
) d 4.45–4.39 (m,
2
H), 4.22 (ddd, 1H, J = 10.2, 9.3, 6.1 Hz), 2.58 (m, 1H), 2.26 (m, 1H).
1
1
H NMR data for lactic acid (3): H NMR (400 MHz, CDCl
H, J = 7.4 Hz), 1.43 (d, 3H, J = 7.4 Hz).
3
) d 4.27 (q,
1
1
1
H NMR data for d
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This journal is ©The Royal Society of Chemistry 2014