Facile Synthesis of Optically-Active Γ-Valerolactone from Levulinic Acid and Its Esters Using a Heterogeneous Enantio-Selective Catalyst

Article abstract of DOI:10.1007/s10562-017-2291-2

Abstract: Optically-active γ-valerolactone was synthesized by the enantio-selective hydrogenations of levulinic acid and its esters. A tartaric acid-NaBr-modified nickel catalyst produced the optically-active γ-valerolactone with a 60% enantiomeric excess (ee), almost quantitative conversion and chemoselectivity. The synthesis of the optically-active γ-valerolactone using the enantio-selective heterogeneous catalyst would be promising for the large-scale industrial production from levulinic acid and its esters, which can be obtained by the acid-catalyzed dehydration of cellulosic fraction of biomass. Graphical Abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-017-2291-2

Catalysis Letters
https://doi.org/10.1007/s10562-017-2291-2
Facile Synthesis of Optically-Active γ-Valerolactone from Levulinic Acid
and Its Esters Using a Heterogeneous Enantio-Selective Catalyst
Tsutomu Osawa1 · Yuya Tanabe1
Received: 20 October 2017 / Accepted: 26 December 2017
© Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
Optically-active γ-valerolactone was synthesized by the enantio-selective hydrogenations of levulinic acid and its esters. A
tartaric acid-NaBr-modified nickel catalyst produced the optically-active γ-valerolactone with a 60% enantiomeric excess
(ee), almost quantitative conversion and chemoselectivity. The synthesis of the optically-active γ-valerolactone using the
enantio-selective heterogeneous catalyst would be promising for the large-scale industrial production from levulinic acid
and its esters, which can be obtained by the acid-catalyzed dehydration of cellulosic fraction of biomass.
Graphical Abstract
Keywords Optically-active γ-valerolactone · Levulinic acid · Alkyl levulinate · Tartaric acid modified Ni · Enantio-
differentiating hydrogenation
1 Introduction
The GVL can be produced by the hydrogenation of alkyl
levulinate or levulinic acid that is obtained by the hydrolysis
of cellulosic biomass [18, 19]. Concerning the production
of the racemic GVL, intensive studies have already been
reported using various homogeneous catalysts [20–23] and
heterogeneous catalysts [24, 25]. Meanwhile, the research
studies for the production of the optically-active GVL have
not made much progress compared to that of the racemic
ones. Especially, the development of enantio-selective het-
erogeneous catalysts has lagged behind the homogeneous
ones [16, 26–29].
The application of γ-valerolactone (GVL) as a sustainable
liquid for carbon-based chemicals was first proposed by Hor-
vath et al. [1]. In recent years, much attention has been paid
for the facile synthesis of GVL for the production of various
kinds of materials. For example, the application of GVL is
a raw material for liquid alkanes [2, 3], and a precursor of
bio-polymers [4–7]. GVL is also proposed as a renewable
solvent [8–12], as well as a fuel additive [1]. Especially, the
optically-active GVL can be a chiral starting compound for
the synthesis of chiral fine chemicals [13–17].
The enantio-selective modified heterogeneous catalysts
(solid catalysts which have an intrinsic catalytic activ-
ity and the surface of which is modified by optically-
active compounds) are promising for the facile industrial
synthesis of optically-active compounds. Modified solid
catalysts have the characteristics of easy and low cost
preparation, easy separation from the reaction mixture,
and easy reuse. The tartaric acid (TA)-NaBr-modified
* Tsutomu Osawa
osawa@sci.u-toyama.ac.jp
1
Graduate School of Science and Engineering for Research,
University of Toyama, Gofuku, Toyama 930-8555, Japan
Vol.:(0123456789)
1 3

T. Osawa, Y. Tanabe
nickel catalyst is one of the successful enantio-selective
heterogeneous catalysts [30, 31]. This catalyst produces a
high enantio-selectivity of over 98% during the hydrogen-
ation of β-ketoesters [32, 33] and 85% during 2-alkanone
hydrogenations [34, 35]. The enantio-selective hydrogen-
ation of levulinic acid and alkyl levulinates to GVL would
be an environmentally benign approach for the efficient
transformation of biomass waste into a value-added chiral
building block.
2.1 Enantio‑Differentiating Hydrogenation of Alkyl
Levulinates
The hydrogenation of the various esters of levulinic acid
was carried out using an in situ modification method, i.e.,
modifier and auxiliary modifier were added to the reaction
media [36, 37]. A 0.94 g sample of nickel oxide (Wako
Pure Chemical Industries, Ltd.) was treated at 623 K for
1 h under a H2 stream (30 mL min−1) to obtain the reduced
nickel catalyst. Sodium bromide in 50 µL H2O and (R,R)-
tartaric acid (TA) (the amounts are stated in the text) were
added to a mixture of levulinate (2.9×10−2 mol), acetic acid
(0.065 g), and the solvent (7 mL). This substrate solution and
the reduced nickel catalyst were placed in a magnetically-
stirred autoclave [OM Lab-Tech Co., Ltd. (Tochigi, Japan)].
Hydrogenation was carried out under the initial hydrogen
pressure of 9 MPa for 20 h. The stirring rate of the autoclave
was 1130 rpm.
In the present study, the enantio-differentiating hydro-
genations of levulinic acid and various alkyl levulinates
(Scheme 1) were carried out over the modified nickel
catalyst. The effects of the catalyst preparation methods
and the hydrogenation conditions on the selectivity and
the enantioselectivity of GVL were investigated.
2 Experimental
2.2 Enantio‑Differentiating Hydrogenation
of Levulinic Acid
Hydrogen gas (99.99%) and nitrogen gas (99.999%) were
obtained from Takachiho Trading Co., Ltd. Ion exchanged
water was used for preparation of the catalysts.
The hydrogenations of levulinic acid were carried out
using an in situ modification method and a pre-modifi-
cation method [38]. The hydrogenation using the in situ
modification was almost the same as that of the alkyl
levulinates. The hydrogenation procedure using a pre-
modification was as follows. A 0.94 g sample of nickel
oxide (Wako Pure Chemical Industries, Ltd.) was treated
at 623 K for 1 h under a H2 stream (30 mL min−1) to
obtain the reduced nickel catalyst. The aqueous solution
of (R,R)-TA and NaBr (the amounts are stated in the text)
Levulinic acid (> 95% Wako Pure Chemical Ind.,
Ltd.) was used after distillation. Methyl levulinate and
ethyl levulinate were synthesized from levulinic acid
and the corresponding alcohols using an ion exchange
resin (Amberlite 15). Propyl, butyl, 1-methyl-propyl,
2-methyl-propyl, and cyclohexyl esters were synthesized
using levulinic acid and the corresponding alcohols and
a Dean–Stark apparatus.
Scheme 1 Enantio-differen-
tiating hydrogenation of alkyl
levulinates and levulinic acid
Major isomer
R: -CH3, -CH2CH3,
-(CH2)2CH3,
-(CH2)3CH3,
Major isomer
1 3

Facile Synthesis of Optically-Active γ-Valerolactone from Levulinic Acid and Its Esters Using…
was adjusted to pH 3.2 using a 1 M NaOH solution (modi-
fication solution). The reduced nickel catalyst was soaked
in the modification solution and stored for 1 h at 373 K.
The catalyst was successively washed with water (10 mL),
twice with methanol (25 mL), and twice with the reaction
solvent (10 mL). The mixture of the levulinic acid, acetic
acid, and the solvent (the amounts are mentioned at the
footnote of the table) and the reduced nickel catalyst were
placed in a magnetically-stirred autoclave [OM Lab-Tech
Co., Ltd. (Tochigi, Japan)]. Hydrogenation was carried out
under the initial hydrogen pressure of 9 MPa for 20 h. The
stirring rate of the autoclave was 1130 rpm.
3 Results
3.1 Enantio‑Differentiating Hydrogenation of Alkyl
Levulinates Over an In Situ Modified Nickel
Catalyst
In order to synthesize the optically-active GVL by the hydro-
genation of alkyl levulinates using an in situ modified nickel
catalyst, the effects of the types of solvent on the hydrogena-
tion rate, the conversion and chemoselectivity, and the ee
were initially examined. In the case of the in situ modifica-
tion method, most of the TA and NaBr added to the reaction
media are adsorbed on the nickel surface during the initial
stage of the reaction [39] as well as the in situ modified
cinchonidine modified Pt catalysts [40, 41]. These modifier
and the auxiliary modifier should be dissolved in the reac-
tion media in order to be uniformly adsorbed on the nickel
surface [37]. This is the reason why NaBr was dissolved in a
small amount of deionized water (50 µL). Table 1 shows the
effects of the types of solvents during the enantio-differenti-
ating hydrogenation of methyl levulinate as a representative
example of the alkyl levulinates.
2.3 Analysis of the Hydrogenated Product
The enantiomeric excess (ee) was determined by GLC.
ꢀ(R) − (S)ꢀ
ee =
(R) + (S)
(R) and (S) are the peak areas of the (R) and (S) enan-
tiomers, respectively. For both the hydrogenations of
levulinic acid and its esters, as the product was mainly
GVL, the ee values were calculated from the peak integra-
tion of the corresponding enantiomers of the GVL. They
were determined without any pre-derivatization of the
hydrogenated product. Analyses were carried out using a
chiral capillary gas chromatograph [Shimadzu GC-18A,
CP Chirasil DEX-CB (0.25 mm × 25 m)] at 333–413 K
(5 K min−1), then at 413–433 K (10 K min−1). The repro-
ducibility of the ee value was with an error of ≤ 2%. The
conversion and lactone selectivity were also determined
by the same column and analysis conditions.
The examined solvents, except for methanol, gave almost
a 100% conversion in a 20-h reaction, although the hydro-
genation rates in the alcoholic solvents were higher than
those in the aprotic solvents. While the selectivity of GVL
was more than 95% for all the solvents, the ee depended
on the types of solvents. Aprotic solvents, such as THF,
1,4-dioxane, and methyl propionate, gave a higher ee than
the alcoholic solvents. As THF produced the highest ee, it
was selected as the solvent in this study.
As has been reported that the addition of NaBr as an
auxiliary modifier increased the ee for the hydrogenations
Table 1 Effects of the types
Solvent
Conversion (%)
Hydrogenation
rate (mmol h−1
Selectivity (%)
ee (%)
of solvents during the enantio-
differentiating hydrogenation of
methyl levulinate
)
GVL
Alcohol
Transesteri-
fied alcohol
THF
100
100
100
82
3
2
2
2
7
7
8
14
5
7
95
99
99
93
96
98
98
98
98
98
5
1
1
7
2
1
1
2
2
1
–
–
–
–
2
1
1
0
0
1
46
40
41
2a
17
27
38
35
39
34
1,4-Dioxane
Methyl propionate
Methanol
Ethanol
99
1-Propanol
2-Poropanol
1-Butanol
2-Butanol
2-Methyl-1-propanol
100
100
100
100
100
NiO 0.94 g (13 mmol), reaction mixture: 29 mmol methyl levulinate, 1.1 mmol acetic acid, 7 mL solvent,
0.025 mmol (R,R)-TA and 5.8×10−3 mmol NaBr in 50 µL H2O. Hydrogenation temperature: 373 K
a(S)-isomer in excess
1 3

T. Osawa, Y. Tanabe
of β-ketoesters and alkanones [42, 43], the effects of the
amount of NaBr added to the reaction media was investi-
gated in the methyl levulinate case. The results are shown
in Fig. 1.
3.2 Enantio‑Differentiating Hydrogenation
of Levulinic Acid Over Modified Nickel Catalyst
The one-pot conversion of levulinic acid to GVL is favorable
for the industrial large-scale synthesis of GVL using lev-
ulinic acid prepared from biomass waste [16]. Table 3 shows
the enantio-differentiating hydrogenation of levulinic acid
over the modified reduced nickel catalyst.
The conversions of 100% were attained by the addition
of 1.5–5.8 µmol NaBr. Less and greater amounts of NaBr
produced lower conversions. In the absence of NaBr or
below 0.5 µmol, almost racemic products were obtained.
The increase in the amount of NaBr increased the ee and
a 5.8 µmol addition resulted in a 46% ee.
In contrast to the hydrogenation of various alkyl levuli-
nates, levulinic acid was difficult to be hydrogenated using
the in situ modified reduced nickel catalyst, i.e., low con-
versions of less than 10% were attained. In contrast, a pre-
modified reduced nickel catalyst attained a much higher
conversion. Hence, the effects of the amount of NaBr in
the modification solution and the amount of acetic acid
in the reaction media were investigated over pre-modified
nickel catalysts. The modification with a solution contain-
ing 5 mmol TA and 22 mmol NaBr, and the addition of
1.7 mmol acetic acid to the reaction mixture produced the
highest ee of 60% with a 100% conversion. The selectivity
of GVL was 100% irrespective of the conversion value. The
effects of the hydrogenation temperature (353–413 K) on the
conversion and the ee were also investigated. The results are
shown in Table 4.
The effects of the hydrogenation temperature from 353
(333) to 413 K were also investigated for the hydrogena-
tion of various alkyl levulinates over the in situ modified
reduced nickel catalyst. Table 2 shows the results.
An over 96% lactone selectivity was attained at > 393 K
for all the substrates (except 2-methyl-propyl levulinate).
The highest ee was attained for the 373–393 K hydrogena-
tion of all the examined substrates. Ester groups with a
longer alkyl chain had a tendency for producing a higher
ee. The highest 60% ee was attained for the n-butyl lev-
ulinate at 373 K. Branching of the alkyl group did not
affect the ee. The ee of the substrates with 2-methyl-propyl
and iso-butyl groups was the same as that with the propyl
group (57% ee).
As in the alkyl levulinate case, a 60% ee was attained at
373 K at 100% conversion. No product other than GVL was
obtained.
4 Discussion
100
The in situ modification method is more attractive for the
synthesis of optically-active compounds in industry than the
pre-modification method, because the independent modifica-
tion process can be omitted and the industrial waste solution
containing nickel ions as heavy metals does not occur. We
previously reported the enantio-differentiating hydrogena-
tion of methyl levulinate over pre-modified Raney nickel
and reduced nickel catalyst, and attained a 51% ee of GVL
using the pre-modified reduced nickel [44]. In this study,
the in situ modified system, which is more preferable for the
industrial production of GVL, was investigated. For attaining
a high ee using the in situ modification method, the modifier
and auxiliary modifier should be completely dissolved in the
reaction media [37]. In this regard, as TA can be dissolved
in the evaluated solvent (Table 1), it can be added to the
reaction media without dissolving in water. On the contrary,
NaBr should be dissolved in 50 µL of water, because of its
low solubility in aprotic solvents such as THF. Based on the
results in Table 1, although the solubilities of TA and NaBr
are higher in alcoholic solvents than in aprotic solvents, the
ee was higher for the aprotic solvents than for the alcoholic
solvents. Among the primary alcohols examined, the alcohol
80
Conversion / %
ee / %
60
40
20
0
0
2
4
6
8
NaBr / µmol
Fig. 1 Effects of the amount of NaBr in the modification solution on
the conversion and the enantio-selectivity. NiO 0.94 g (13 mmol),
reaction mixture: 29 mmol methyl levulinate, 1.1 mmol acetic acid,
7 mL THF, 0.025 mmol (R,R)-tartaric acid, and NaBr in 50 µL H2O.
Hydrogenation temperature: 373 K
1 3

Facile Synthesis of Optically-Active γ-Valerolactone from Levulinic Acid and Its Esters Using…
Table 2 Enantio-differentiating
Substrate
Hydrogenation tem-
perature (K)
Conversion (%)
Lactone selectiv- ee (%)
ity (%)
hydrogenation of various
4-oxopentanoates
CH3CO(CH2)2COO–
–CH3
333
353
373
393
413
353
373
393
413
353
373
393
413
353
373
393
413
353
373
393
413
353
373
393
413
353
373
393
413
3
29
100
100
100
22
38
64
93
97
98
52
91
98
99
74
88
97
98
51
86
96
97
16
52
89
100
54
78
96
97
58
81
96
99
25
35
46
44
42
35
48
53
49
40
54
57
50
46
60
59
53
41
55
57
52
45
57
57
48
52
59
59
53
–CH2CH3
29
100
100
22
–(CH2)2CH3
59
100
100
37
–(CH2)3CH3
95
100
100
23
52
97
100
19
69
100
100
24
–CH(CH3)CH2CH3
–CH2CH(CH3)2
–Cyclohexyl
82
97
100
NiO 0.94 g (13 mmol), reaction mixture: 29 mmol levulinic acid ester, 1.1 mmol acetic acid, 7 mL THF,
0.025 mmol (R,R)-TA and 5.8×10−3 mmol NaBr in 50 µL H2O
with a longer alkyl chain gave a higher ee. The secondary
alcohol produced a higher ee than the primary alcohol.
These tendencies were the same as the methyl acetoacetate
case [45–47], and indicated that the effective stronger inter-
actions between the TA and substrate by hydrogen bond and
ion–dipole interaction (TA is actually adsorbed as a sodium
salt [48]) were achieved in the aprotic solvent.
50]. However, it was revealed that the effects of the addi-
tion of NaBr during the hydrogenation of methyl levuli-
nate were more significant than for the methyl acetoacetate
case. An almost racemic product was produced without
the addition of NaBr to the reaction system, meanwhile,
the addition of a small amount significantly increased the
ee. As the addition of 2.9 × 10−6 mol of sodium 2-eth-
ylhexanoate instead of NaBr also increased the enantio-
selectivity to 16%, the sodium ion would play an essential
role in the enantio-differentiation of the prochiral face of
methyl levulinate [48]. As the addition of NaBr attained a
higher ee than that of sodium 2-ethylhexanoate, Br− also
contributed to increasing the enantio-selectivity. The role
of Br− would be the same as the hydrogenation of methyl
acetoacetate, i.e., blocking the hydrogenation on the non-
enantio-differentiating sites where racemic products were
produced [38, 51].
Optimization of the amount of NaBr in the modifica-
tion process is also of critical importance for attaining a
high ee when reduced nickel was used as the base nickel
material, because its optimal amount depended on the
manufacturer or even the lot number of the nickel oxide, a
precursor of the reduced nickel catalyst [44]. The effects
of the amount of NaBr for the hydrogenation of methyl
levulinate over the in situ modified nickel catalyst (Fig. 1)
showed a tendency similar to the hydrogenation of methyl
acetoacetate using the pre-modified Raney nickel [42, 49,
1 3

T. Osawa, Y. Tanabe
Table 3 Enantio-differentiating hydrogenation of levulinic acid over
mechanism could be changed according to the hydrogena-
tion temperature. The studies of this aspect are now in pro-
gress. The 60% ee was attained for the hydrogenation of
butyl levulinate, which was the highest value attained by the
enantio-selective heterogeneous catalyst reported, to the best
of our knowledge.
modified Ni catalyst
Modi-
TA (mmol) NaBr
(mmol)
Acetic
acid
Conv. (%) ee (%)
fication
method
(mmol)
in situa
in situa
preb
0.025
0.025
5.8×10−3
1.1c
1.7d
1.7e
1.7e
1.7e
1.7e
0e
8
4
100
100
97
13
28
10
20
60
47
53
60
55
58
43
30
5.8×10−3
As for the hydrogenation of levulinic acid using the in situ
modification method, a lower conversion was attained com-
pared to the alkyl levulinate case. This would be attrib-
uted to the acid characteristics of the substrate. Levulinic
acid would be competitively adsorbed on the nickel sur-
face with TA during the initial stage of the reaction. Large
amount of levulinic acid (8.6×10−3 mol) compared to TA
(2.5×10−5 mol) in the reaction mixture would hinder the TA
adsorption. It is known that modification of the nickel sur-
face by TA increases the hydrogenation rate [52]. Therefore,
the decrease in the amount of TA could result in a decreased
conversion and ee. Meanwhile, the pre-modification method,
by which TA is firmly adsorbed before the reaction in the
appropriate surface coverage, afforded almost quantitative
conversions. Concerning the effects of the addition of acetic
acid to the reaction media, it was reported that the acetic
acid accelerated the hydrogenation rate on the enantio-dif-
ferentiating sites through the interaction with TA, which was
revealed during the hydrogenation of methyl acetoacetate
[52]. This could be also applied to the hydrogenations of
levulinate and levulinic acid. The results that the hydrogena-
tion rate of levulinic acid was higher than that of levulinate
(Tables 2, 3) partly support the above idea. The carboxyl
acid with smaller alkyl group (acetic acid) was effective for
increasing in ee with a smaller amount of the acid com-
pared to the carboxylic acid with larger alkyl group (pivalic
acid) [44]. This could explain the present results that small
amount of acetic acid increased the ee in the hydrogenation
of levulinic acid. The highest ee of 60% with a 100% conver-
sion was attained for the enantio-differentiating hydrogena-
tion of levulinic acid as well as the alkyl levulinate. This is
also the highest value so far obtained over the heterogeneous
enantio-selective catalyst.
5
5
5
5
5
5
5
5
5
5
0
preb
7.3
22
51
22
22
22
22
22
22
preb
preb
41
preb
100
100
99
93
100
96
preb
1.7e
3.3e
5.0e
6.7e
8.3e
preb
preb
preb
preb
aModification reagents were added to the reaction mixture
bModification solution: 5 mmol (R,R)-TA and NaBr in 75 mL H2O
(pH 3.2, 373 K)
cReaction mixture: 29 mmol levulinic acid, 1.1 mmol acetic acid,
7 mL THF, 0.025 mmol (R,R)-TA, and 5.8×10−3 mmol NaBr in
50 µL H2O
dReaction mixture: 8.6 mmol levulinic acid, 1.7 mmol acetic acid,
10 mL THF, 0.025 mmol (R,R)-TA, and 5.8×10−3 mmol NaBr in
50 µL H2O
eReaction mixture: 8.6 mmol levulinic acid, acetic acid, and 10 mL
THF.
Hydrogenation temperature: 373 K
Table 4 Effects of the hydrogenation temperature on the conversion
and ee during the hydrogenation of levulinic acid
Hydrogenation temperature
(K)
Conversion (%)
ee (%)
353
373
393
413
77
97
100
100
56
60
55
39
NiO 0.94 g, modification solution: 5 mmol (R,R)-TA and 22 mmol
NaBr in 75 mL H2O (pH 3.2, 373 K), reaction mixture: 8.6 mmol lev-
ulinic acid, 1.7 mmol acetic acid, and 10 mL THF
The direct asymmetric reduction of levulinic acid and
its esters to GVL is rather difficult even using homogene-
ous catalysts compared to the reductions of α-ketoesters,
α-ketoacids, and β-ketoesters. For example, 82% ee was
attained by the hydrogenation of levulinic acid over the
ruthenium complex at 423 K [16], while the hydrogenation
of the α-ketoesters and β-ketoesters produced more than
a 95% ee at 298 K [41, 53] and 337 K [54], respectively.
Although the ee obtained by the TA-NaBr-modified nickel
catalyst was now rather lower (60%) than those obtained by
the homogeneous complex catalysts, this value was attained
at 373–393 K with an almost quantitative chemoselectivity
and conversion, as well as having the typical advantages of
heterogeneous catalysts, i.e., easy preparation, easy recovery
Concerning the effects of the hydrogenation temperature
during the hydrogenation of various alkyl levulinates, the
higher ee was attained at 373–393 K than at 353–413 K for
each substrate. This tendency was different from our previ-
ous results over the modified Raney nickel catalyst (ee was
independent of the hydrogenation temperature [44]). This
could be partly attributed to the difference in the hydro-
genation activity of the catalyst. The hydrogenation activ-
ity of the modified reduced nickel is lower than that of the
modified Raney nickel catalyst. The enantio-differentiating
1 3

Facile Synthesis of Optically-Active γ-Valerolactone from Levulinic Acid and Its Esters Using…
13. Gorissen HJ, Van Hoeck J-P, Mockel AM, Journée GH, Delatour
and reuse, and particularly, resource savings (not using pre-
cious metals for the present catalyst). As for the isolation
of GVL from the product solution, almost the quantitative
yield of GVL was attained after the removal of the catalyst
using magnet and a simple distillation, in the case of the
conversion and the chemoselectivity of GVL was 100%.
The study of the development of the catalyst for ring clo-
sure of alkyl 4-hydroxypentanoate is in progress. Hence, the
TA-NaBr-modified nickel catalyst would be promising for
the industrial production of the optically-active GVL from
bio-mass waste.
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The optically-active GVL was synthesized by the enantio-
selective hydrogenations of levulinic acid and its esters,
which can be obtained by the degradation of biomass. The
optically-active GVL with 60% ee was produced from both
levulinic acid and its esters in almost quantitative conversion
and chemoselectivity using the TA-NaBr-modified nickel
catalyst. The enantio-selective hydrogenation of levulinic
acid required a pre-modified catalyst. This would be attrib-
uted to the acid characteristics of the substrate. Meanwhile,
the enantio-selective hydrogenations of alkyl levulinates
proceeded by the in situ modified catalysts, which is more
favorable for the industrial applications. The synthesis of
optically-active GVL from levulinic acid and its esters using
enantio-selective heterogeneous catalysts would be promis-
ing for its large-scale industrial production.
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