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DOI: 10.1039/C4GC02006E
COMMUNICATION
Zemplén Transesterification: A Name Reaction Having

Been Misleading Us for 90 Years
Cite this: DOI: 10.1039/x0xx00000x
Bo Ren,a Meiyan Wang,b Jingyao Liu,b Jiantao Ge,a Xiaoling Zhanga and Hai Donga,*
Green Chemistry Accepted Manuscript

Published on 24 November 2014. Downloaded by Northeastern University on 27/11/2014 12:25:06.
Received 00th January 2014,

Accepted 00th January 2014
DOI: 10.1039/x0xx00000x
www.rsc.org/greenchem
We demonstrated that using NaOH and NaOMe in methanol In this study, we proved that Zemplén condition had been
for deacylation are identical, indicating that Zemplén misleading us for almost 90 years. We found that deacylation using a
condition has been misleading us for almost 90 years. The hydroxyl anion base in methanol does not in fact require a
traditional base-catalyzed mechanism cannot be used to stoichiometric amount of base for each ester functional group. The
explain our results. We proposed that H-bond complexes play results of our experiments indicate that the use of NaOH in methanol
key roles in the base-catalyzed process, explaining why is identical to that of NaOMe in methanol for deacylation. The
deacylation in methanol can be catalyzed by hydroxide. development of Zemplén condition was based on the tranditional
base-catalyzed mechanim which cannot be used to explain our
Acyl groups are widely used as protecting groups in organic results (Figure 1a). Therefore, deacylation can be performed with a
synthesis strategies, especially in carbohydrate chemistry.[1] With the catalytic amount of hydroxyl anion resin and the resin can be
addition of acylation reagents under mild conditions, the hydroxyl repeatedly reused in the same process after simply filtered. These
groups of substrates readily form esters as intermediate products, and results cannot be explained by traditional base-catalyzed mechanism.
the esters are easily removed under Zemplén conditions when We proposed that H-bond complex play key roles in this base-
required.1-2 For almost 90 years, it has been believed that the regular catalyzed process (Figure 1b), supported by theoretical studies. An
hydrolysis of an ester using a base such as potassium hydroxide inverse kinetic isotope effect (KIE) may give direct evidences to
(KOH) or sodium hydroxide (NaOH) requires a stoichiometric support the H-bond involved principle. Therefore, the tranditional
amount of base for each ester functional group, and generates a large base-catalyzed principle in textbook might be discarded.
amount of potassium or sodium acetate, whereas Zemplén
deacylation uses only a catalytic amount of sodium methoxide
(NaOMe).2 Today, Zemplén deacylation, performed with a catalytic
amount of sodium methoxide in methanol, is a standard tool in
laboratories and industry settings.1 Its inherent disadvantage is the
retention in solution of sodium ions. As the sodium ions can be
removed using H+-exchanged resin, industrial deacylation
techniques normally involve ion-exchanged columns. The H+-
exchanged resin can be regenerated with acid after ion exchange.
The ion exchange procedure would be omitted from deacylation in
laboratories, and especially in industry settings, supposed that the
reaction were catalyzed by methoxyl anion resin. At first appearance,
it seems impossible due to the difficulty of acquiring methoxyl anion Figure 1. a) Traditional mechanism of deacylation catalyzed by hydroxyl anion. b)
Our proposed mechanism of deacylation catalyzed by H‐bond complex.
resin. In 1981, Goodman’s group found that hydroxyl anion
exchanged resin could be used for the catalytic deacylation of sugars
in methanol.3 They believed that the deacylation be catalyzed by We were surprised to find that the penta-acetyl glucosides were
methoxyl anion and the methoxyl anion be generated by a series of completely deacetylated by 0.1 equiv. of NaOH in methanol. Indeed,
ion exchanges with the hydroxyl anion at the resin surface. Despite only 0.02 equiv. of NaOH was used for each ester functional group
its reported efficiency,4 this method has unfortunately not been of the glucoside. At first, this result seemed impossible due to the
extensively adopted, likely because of the unconvincing explanation. preconception that deacylation with NaOH in methanol requires a
This journal is © The Royal Society of Chemistry 2014 Green Chemistry, 2014, 00, 1‐3 | 1
Green Chemistry Page 2 of 29
COMMUNICATION Green Chemistry
stoichiometric amount of base for each ester functional group, and Table 2. Deacylation catalyzed by NaOMe, NaOH or –OH-resin.
generates a large amount of sodium acetate. To clarify the result, e
Entry Substrate Product Yield
View Article Online
additional experiments were conducted to compare the use of NaOH DOI: 10.1039/C4GC02006E
with that of NaOMe: 0.1, 0.02 and 0.01 equiv. of each of the two
bases was used to deacetylate glucoside 1 (entries 1 and 2 in Table 1a,b Quant
1). The free glucoses 2 were obtained in quantitative yields in 0.5 h.
and 4 h. with the use of 0.1 and 0.02 equiv., respectively, of either
NaOH or NaOMe. When the amount of either base was decreased by
2a,b Quant
0.01 equiv., the deacetylation of glycoside 1 remained incomplete
until 24 hours. These results indicate that the use of NaOH in
methanol is identical to the use of NaOMe in methanol for the
deacylation of glucoside 1. In the following experiments, various 3a,b Quant

bases including KOH, sodium sulfide (Na2S), potassium sulfide
(K2S), sodium carbonate (Na2CO3), potassium carbonate (K2CO3),
calcium oxide (CaO) and magnesium oxide (MgO), were used as

catalysts (entries 3-9 in Table 1). The deacetylation of 1 was 4a,b Quant
completed in 0.5 h. with 0.1 equiv. of KOH; in 1 h. with 0.1 equiv.
of Na2S and K2S; in 4 h. with 0.1 equiv. of Na2CO3 and K2CO3; and
in 8 h. with 0.2 equiv. of CaO. With 0.2 equiv. of MgO, the
deacetylation remained incomplete until 24 hours. These results
indicate that it is incorrect to assume that deacetylation can only be 5a,b Quant
catalyzed by the methoxyl anion in methanol. Dry methanol has
traditionally been used as the solvent on the grounds that any water
in the methanol will consume the NaOMe, thereby preventing
6a,b Quant
deacetylation. However, our experiments showed that water has little
effect on the deacetylation (entries 10 and 11 in Table 1). With 0.1
equiv. of NaOH or NaOMe, the deacetylation of 1 was completed in
0.5 h. and 1 h. when the methanol contained 1% and 10% of water, 7a Quant
respectively. The deacetylation achieved around 60% completion
(observed from TLC plate) even when the methanol contained 50%
of water. 8a Quant
Table 1. Deacylation of penta-acetyl glucoside 1 catalyzed by various bases.a
9c Quant
10d Quant
b
Entry Base Amount (eq.) Time/h Yield
0.1 0.5 Quant.
Reagents and conditions: [a] substrates (100 mg), NaOMe or NaOH (0.1 eq.),
1 NaOMe 0.02 4 Quant.
MeOH (1 mL), rt.; [b] substrates (100 mg), hydroxyl anion resin (85 mg/ 0.1
0.01 24 -c
eq.), MeOH (1 mL), rt.; [c] substrates (100 mg), NaOMe or NaOH (1.1 eq.),
0.1 0.5 Quant.
MeOH (1 mL), rt.; [d] substrates (100 mg), NaOMe or NaOH (2.1 eq.), MeOH
2 NaOH 0.02 4 Quant.
(1 mL), rt.; [e] NMR yield. Isolation yield > 90%.
0.01 24 -c
3 KOH 0.1 0.5 Quant.
4 Na2S 0.1 1 Quant. In the further experiments, various substrates including the penta-
5 K2S 0.1 1 Quant. acetyl/benzoyl-galactosides 3, glucosides 5 and mannosides 6, and
the methyl tetra-acetyl-galactosides 8,-glucosides 9,-
6 Na2CO3 0.1 4 Quant.
galactosides 12,-glucosides 13 and-mannosides 16, were
7 K2CO3 0.1 4 Quant.
deacylated in methanol using 0.1 equiv. of NaOH and NaOMe
8 CaO 0.2 8 Quant.
separately. It showed that (Table 2), irrespective of whether NaOH
9 MgO 0.2 24 -c or NaOMe was used, the deacetylated free glycosides were obtained
1/100 0.5 Quant. from the acetylated substrates in quantitative yields in 2 - 12 h.
10d NaOMe 10/90 1 Quant.
50/50 24 -c Additional experiments were conducted to compare the use of NaOH
1/100 0.5 Quant. and NaOMe in the deprotection of benzyloxycarbonyl and pivaloyl
11d NaOH 10/90 1 Quant. groups. All of the deprotections were completed in 2 h. In the case of
50/50 24 -c the deacylation of acetylated thio-containing glycosides, a little more
[a]
Reagents and conditions: substrates (100 mg), MeOH (1 mL), rt.; [b] NMR than a stoichiometric amount of the base is necessary for each
yield; [c] uncompleted deacylation; [d] bases (0.1 eq.), addition of water (1 - thioacetate group because the sulfhydryl group formed will
50%).
2 | Green Chemistry, 2014, 00, 1‐3 This journal is © The Royal Society of Chemistry 2014

Green Chemistry COMMUNICATION
neutralize the base. Therefore, 1.1 equiv. and 2.1 equiv. of NaOMe in Figure 3b: deacylation is catalyzed by the hydroxyl anion to form
were used in the deacetylation of penta-acetyl 1-thio-glucoside 20 an acetate anion, followed by esterification of methanol with the
View Article Online
and methyl tetra-acetyl 2,4-dithio-glucoside 22, producing free thioacetate anion. However, as the esterification of methanol does not
DOI: 10.1039/C4GC02006E
glucosides in quantitative yields in 2 h, respectively. Testing NaOH occur when sodium acetate is dissolved in methanol, path b is also
with these substrates gave the same results. The results of all of these excluded. The above analyses indicate that transesterification
experiments indicate that the use of NaOH is identical to the use of catalyzed by hydroxyl cannot be explained by traditional base-
NaOMe. As the effects on deacylation of using NaOH in methanol catalysis principle.
and NaOMe in methanol are identical, it is reasonable that hydroxyl a) MeOH + -OH MeO- + H2O
anion resin is used in deacylation instead of NaOH. When hydroxyl
-
anion resin was used in the deacylation of each of compounds 3, 5, 6, O O- H2O OH
8, 9, 12, 13, 16, 18 and 19, all of the deacylations were completed in R R
R HO
O MeO O
2-12 h. As hydroxyl anion resin is a catalyst, we hypothesized that it MeO-
MeOAc

should be reused repeatedly in this process without time restrictions.
To test this assumption, we used hydroxyl anion resin (425 mg, 1
equiv. for the substrate but 0.2 eq. for each of the acetyl groups) to b)
deacetylate penta-acetyl glucoside 1 (100 mg) in 1 mL of methanol O O- AcOH AcO-
R
with stirring. The first deacetylation was completed in 0.5 h. After R
O
R HO
O HO
-
filtration, the resin was reused. The second deacetylation was HO
AcOH
completed in 1 h. With repetition, the deacetylation extended the
reaction time to 2, 2.5, 3, 4 and 5 h, until the seventh deacetylation
MeOH + AcO- MeOAc + -OH
(a in Figure 2). We suspected that tiny chips of hydroxyl anion
Figure 3. Proposed two possible transesterification paths catalyzed by hydroxide
chipped from the resin surface by stirring had reduced the catalytic in light of traditional base‐catalysis principle.
activity of the resin. Therefore, no stirring took place in the
subsequent experiments, during which deacetylation extended the
Recently, a principle that hydrogen bonds between hydroxyl groups
reaction time from 0.5 to 2 h, with repetition until the 10th
and acetate anions involve the constitution of the rate-determining
deacetylation (b in Figure 2), confirming our conjecture.
transition state structure in pyridine catalyzed acetylation of
hydroxyl groups has been widely accepted with the theoretical
OAc OH chemistry studies on the mechanism.5 In our previous studies, we
-
AcO O OH resin HO O have developed new and improved reaction routes where
1 2
AcO OAc MeOH HO OH intermolecular non-covalent forces play key roles.6-8 The mechanism
OAc OH
studies also showed that the hydrogen bonds between hydroxyl
group and anions play key roles in the intramolecular acetyl group
migration6 and the regioselective acetylation catalyzed by acetate
anions8. These results inspired us to propound that the H-bonds
between hydroxyl groups and anions must also play key roles in
deacylation. Only the principle involving H-bond could perfectly
explain all our experimental results obtained in this study. Thus,
during deacylation catalyzed by NaOMe, an H-bond complex
[MeOH…..OMe]- may instantly form when a catalytic amount of
NaOMe is dissolved in methanol without considering about
solvation (a in Figure 4). Then the acetyl group is transformed into
methoxide through transition state a. During deacylation catalyzed
by NaOH, an H-bond complex [MeOH…..OH]- may instantly form (b
in Figure 4). Then it has to be hypothesized that the energy barrier of
transition state b lower than that of transition state c so that the
Figure 2. Deacetylation with the repeated reuse of a catalytic amount of –OH‐ acetyl group can be transformed into methoxide through transition
exchange resin. state b; otherwise the acetyl group would be transformed into
hydroxide through transition state c so as to restrain the catalytic
The process by which hydroxyl anion catalyzes deacylation is of process. In order to support this, the theoretical calculations were
interest. According to the traditional base-catalysis principle (Figure performed (Figure S7). In order to simplify the calculation, the
1a),2 there are only two possible reaction paths (Figure 3). One deacetylations of ethyl acetate catalyzed by methoxide and
possibility is the reaction path proposed by Goodman3 and shown in hydroxide in methanol were as models for DFT calculations without
Figure 3a: the hydroxyl anion first deprotonates methanol to form considering about solvation. The energy barrier of ethyl acetate with
the methoxyl anion, followed by deacylation catalyzed by the [MeO…..H…..OMe]- for transesterification is 19.9 kcal/mol (Figure
methoxide formed. If this were the case, the addition of water should 4a). The process with [MeO…..H…..OH]- involves two pathways with
restrain the formation of methoxyl anion so as to stop the reaction. energy barriers of 18.4 and 21.1 kcal/mol, respectively, giving the
Thus, the experimental results of adding water (entries 10 and 11 in former process be preferred (Figure 4b).
Table 1) proved this path inefficient. The other possibility is shown
COMMUNICATION Green Chemistry
that the Zemplén condition has been misleading us for almost

90 years and methoxide can be completely replaced by
View Article Online
hydroxide in the deacylation. The traditional base-catalyzed
DOI: 10.1039/C4GC02006E
mechanism can not be used to explain our results. We proposed
that H-bond play key roles in this base-catalyzed process. Both
kinetic isotope effect (KIE) studies and theoretical calculations
may support this principle. Therefore, hydroxyl anion
exchanged resin as a catalyst is used in deacylation instead of
NaOMe or NaOH which is fully supported by theory. The resin
can be repeatedly reused in the same process without additional
treatment. We believe that application of hydroxyl anion in
deacylation has great theoretical and practical significance in

both laboratory and industry settings. With the use of hydroxyl
anion resin in industry, the H+-exchange columns in deacylation
may be reduced, and substantial savings may be made in terms

of equipment, materials and operations.
Acknowledgements
Figure 4. Proposed transesterification paths catalyzed by –OH and MeO‐ via the This study was supported by the National Nature Science
H‐bond complex. Foundation of China (Nos. 21272083). The authors are also
grateful to Dr. Shitao Fu in the Analytical and Test Center of
It is known that an inverse secondary isotope effect would be led School of Chemistry & Chemical Engineering for support with
when the bending vibration of OH bonds in transition state become the NMR instruments.
more restricted.9 Clearly, the bending vibration of OH bonds in
transition states a and b, which are the rate-determining transition Notes and references
state structures (Figure 4), become more restricted due to involving a
School of Chemistry & Chemical Engineering, Huazhong University of
H-bond, thus leading to inverse secondary isotope effects. Thus, an Science & Technology, Luoyu Road 1037, 430074, Wuhan, P.R. China.
inverse kinetic isotope effect (KIE) may give direct evidences to Fax: (+86) 27-87793242, E-mail: [email protected].
support the H-bond involved principle. We chose two simple b
Institute of Theoretical Chemistry, State Key Laboratory of Theoretical
molecules, ethyl benzoate and phenylmethyl acetate, as models, and and Computational Chemistry, Jilin University,Liutiao Road 2,
measured their KIE values through the measurement of their rate
Changchun, 130023, P. R. China.
constants for deacylation catalyzed separately by NaOH and NaOMe
† Supplementary Information (ESI) available: [General methods, general
in normal methanol and d-methanol (Figure S1-S4). For both of the
method for measuring KIE values, Figure S1-S6, computational methods,
model molecules, the measured KIE values (kH/kD) were less than
and Cartesian coordinates, energies and results of frequency calculations].
0.5 (Figure S3 and S4), irrespective of whether NaOH or NaOMe
See DOI: 10.1039/c000000x/
was used, showing inverse secondary isotope effects. The 1H NMR
spectrum of deacylation catalyzed by NaOH showed only the esters
that functioned as starting materials (ethyl benzoate and 1 P. K. Kancharla, T. Kato, D. Crich, J. Am. Chem. Soc. 2014, 136,
phenylmethyl acetate), the esters formed by transesterification 5472; X. Meng, W. L. Yao, J. S. Cheng, X. Zhang, L. Jin, H. Yu, X.
(methyl benzoate and methyl acetate) and the alcohols produced Chen, F. S. Wang, H. Z. Cao, J. Am. Chem. Soc. 2014, 136, 5205; S.
(enthanol and phenylmethanol) (Figure S5 and S6). No acids formed Y. Nie, W. Li, B. Yu, J. Am. Chem. Soc. 2014, 136, 4157; B. J.
by hydrolysis could be seen, indicating that the outcomes of the Beahm, K. W. Dehnert, N. L. Derr, J. Kuhn, J. K. Eberhart, D.
transesterifications were identical to those of NaOMe-catalyzed Spillmann, S. L. Amacher, C. R. Bertozzi, Angew. Chem. Int. Ed.
deacylation. 2014, 53, 3347; Y. Hsu, H. H. Ma, L. S. Lico, J. T. Jan, K. Fukase,
In this study, all the yields reported were based on NMR analysis. Y. Uchinashi, M. M. Zulueta, S. C. Hung, Angew. Chem. Int. Ed.
In order to demonstrate the potential for industry, penta-acetyl- 2014, 53, 2413.
glucoside 1 (10g) were deacylated in methanol (100 mL) using 0.1 2 Z. Wang, Comprehensive Organic Name Reactions and Reagents,
equiv. of NaOH (105 mg), KOH (144 mg) and hydroxyl anion resin John Wiley & Sons, Inc., Hoboken, NJ, 2009.
(8.5 g) separately. After stirring at room temperature for 2 hours 3 L. A. Reed, III, P. A. Risbood, L. Goodman, J. Chem. Soc. Chem.
(experiments in detail in SI), the free glucoses 2 were obtained in Commun. 1981, 760.
92% (4.24 g), 97% (4.48 g) and 89% (4.1 g) isolation yields 4 V. Jaouen, A. Jegou, L. Lemee, A. Veyrieres, Tetrahedron 1999, 55,
respectively. 9245; L. Charon, J.-F. Hoeffler, C. Pale-Grosdemange, M. Rohmer,
Tetrahedron Lett. 1999, 40, 8369; D. Redoules, J. Perie,
Conclusions Tetrahedron Lett. 1999, 40, 4811.
We have shown that using NaOH in methanol and using 5 R. Nishino, T. Turuta, K. Kan, M, Sato, M. Yamanaka, T. Sasamori,
NaOMe in methanol for deacylation are identical. It indicates N. Tokitoh, T. Kawabata, Angew. Chem. Int. Ed. 2013, 52, 6445; P.
4 | Green Chemistry, 2014, 00, 1‐3 This journal is © The Royal Society of Chemistry 2014

Green Chemistry COMMUNICATION
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View Article Online
DOI: 10.1039/C4GC02006E
Table of content:

We demonstrated -OH as deacylation catalyst in methanol, indicating that Zemplén condition had
been misleading us for almost 90 years.
View Article Online

DOI: 10.1039/C4GC02006E
Supporting Information

Zemplén Transesterification: A Name Reaction Having Been Misleading Us for 90
Years
Bo Rena, Meiyan Wangb, Jingyao Liub, Jiantao Gea, Xiaoling Zhanga and Hai
Donga,*
a
School of Chemistry & Chemical Engineering, Huazhong University of Science & Technology, Luoyu Road 1037,
430074, Wuhan, P.R. China, [email protected]
b
Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin
University, Liutiao Road 2, Changchun, 130023, P. R. China.
Contents
General methods S2
General Method for Measuring KIE Value (Figure S1-2) S12
Figure S3 and S4 S13
Figure S5 and S6 S14
Computational methods and Figure S7 S15
References S16
Cartesian coordinates and total energies S16
S1
View Article Online

DOI: 10.1039/C4GC02006E
General methods: All commercially available starting materials and solvents were of
reagent grade and used without further purification. Chemical reactions were monitored
with thin-layer chromatography using precoated silica gel 60 (0.25 mm thickness) plates
(Macherey-Nagel). Flash column chromatography was performed on silica gel 60 (SDS
0.040-0.063 mm). 1H NMR and 13C NMR spectra were recorded at 298K in CDCl3, D2O,
CD3OD and d6-DMSO using the residual signals from CHCl3 (1H:  = 7.25 ppm; 13C:  =
77.2 ppm), D2O (1H:  = 4.80 ppm), CD3OD (1H:  = 3.31 ppm; 13C:  = 49.1 ppm) and

d6-DMSO (1H:  = 2.50 ppm; 13C:  = 39.5 ppm) as internal standard. 1H peak
assignments were made by first order analysis of the spectra, supported by standard 1H-
1
H correlation spectroscopy (COSY).
General Deacylation Catalyzed by NaOH or NaOMe: carbohydrate substrates (100

mg) in dry methanol (1 mL) were added NaOH or NaOMe (0.1 eq.). The mixtures were
stirred at room temperature for 2 - 12 h, followed by ion exchange with H+ exchanged
resin. After being filtered, the filtrate was concentrated to afford the products. All the
products 2, 4, 7, 10, 11, 14, 15, 17 and 21 are known compounds.
General Deacylation Catalyzed by -OH exchanged resin: carbohydrate substrates (100

mg) in dry methanol (1 mL) were added -OH exchanged resin (85 mg). The mixtures
were stirred at room temperature for 2 - 12 h. After being filtered, the filtrate was
concentrated to afford the products.
Large Scale: penta-acetyl-glucoside 1 (10g) were deacylated in methanol (100 mL) using
0.1 equiv. of NaOH (105 mg), KOH (144 mg) and hydroxyl anion resin (8.5 g) separately.
After stirring at room temperature for 2 hours, the reaction mixtures were treated with H+
exchanged resin until neutrality (it is not necessary for reaction mixture with hydroxyl
anion resin as a catalyst). After being filtered, the filtrate was concentrated and
crystallized. The free glucoses 2 were obtained in 92% (4.24 g), 97% (4.48 g) and 89%
(4.1 g) yields respectively.
1-Thio-β-D-mannopyranose 21[1]: Compound 20 (101 mg, 0.25 mmol) was dissolved in

3 mL dry MeOH, and sodium hydroxide (11 mg, 0.27 mmol) in methanol (1 mL) was
added dropwise. After 40 minutes, the reaction mixture was neutralized with Amberlite
IR-120 H+ ion exchange resin, filtered, concentrated in vacuum, and lyophilized to
afford compound 2 (48.5 mg, 99%). 1H NMR (400 MHz, D2O) δ = 5.05 (d, J = 1.0, 1H,
H-1), 4.26 (dd, J=1.0 Hz and 3.1 Hz, 1H, H-2), 4.00 (dd, J=2.2 Hz, 12.4 Hz, 1H, H-3),
3.82 (dd, J = 5.9 Hz, 12.4 Hz, 1H, H-6), 3.74 (dd, J = 3.2 Hz, 9.6 Hz 1H, H-6’), 3.69 (t, J
= 9.4 Hz, 1H, H-4), 3.57–3.48 (m, 1H, H-5).
S2
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DOI: 10.1039/C4GC02006E
Methyl 2,4-thio-β-D-mannopyranoside 23: 1H NMR (400 MHz, CDCl3) δ = 4.51 (s, 1H,
H-1), 3.94 (dd, J = 12.2, 2.1, 1H, H-6), 3.83 (dd, J = 4.6 Hz and 12.2 Hz, 1H, H-6’), 3.57
(m, 2H, H-2, H-3), 3.48 (s, 3H, OMe), 3.35 (s, 1H, OH), 3.29–3.21 (m, 1H, H-5), 3.12 –
2.97 (m, 1H, H-4), 2.77 (s, 1H, OH), 1.72 (d, J = 6.3 Hz, 1H, SH), 1.59 (d, J = 8.2 Hz,
1H, SH). 13C NMR (100 MHz, CDCl3) δ = 100.8, 78.6, 74.0, 62.6, 57.1, 47.3, 39.4.
HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C7H14O4S2Na 249.0231; found 249.0226.

S3
View Article Online

DOI: 10.1039/C4GC02006E
Comparison of 1H NMR spectrum (H1 peak) of crude product from deacylation with
that of reagent grade sample indicating a quantitative NMR yield: carbohydrate
substrates (100 mg) in dry methanol (1 mL) were added NaOH (0.1 eq.). The mixtures
were stirred at room temperature for 2, followed by ion exchange with H+ exchanged
resin. After being filtered, the filtrate was concentrated and directly tested by NMR
instrument.

Deacylation of compound 3 (tested in D2O): a) reagent grade sample; b) crude product.
H1β
H1α a
H1β
H1α b
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H1β
a H1α
H1β
b H1α
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H1α
H1β
a
b
H1α
H1β
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Deacylation of compound 8 (tested in d6-DMSO): a) reagent grade sample with

addition of a drop of D2O; b) reagent grade sample; c) crude product.

a
a
H1
H1 b
c
H1
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a
H1
a
H1
b
H1
c
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a

H1
H1
H1
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a

H1
H1
H1
c
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Deacylation of compound 9, 18 and 19 (tested in d6-DMSO): a) reagent grade

sample with addition of a drop of D2O; b) reagent grade sample; c) crude product for
compound 18; d) crude product for compound 19; e) crude product for compound 9.

a

H1
a
H1
b
H1
H1
d
H1
e
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General Method for Measuring KIE Value: As step b) is the rate-determining step,
the rate constants can be measured using the following equation: ln (B0/B) = k*A*t,
where A stands for the concentration of base catalysts, B stands for the concentration
of esters, k stands for the rate constant, and t is the reaction time. The values of B0/B
can be measured over time using 1H NMR tests. In Figure S1, A stands for the

concentration of the H-bonding complex and X stands for MeO or OH group. As
methanol acts as solvent in the reaction, A equals to the concentration of hydroxyl

anion or methoxyl anion and is a constant. Therefore, we can get the differential
equation (1) which is related to the rate constant k and the concentration of the esters
(B). To solve the differential equation (1) gets equation (2). B0 stands for the initial
concentration of the esters in equation (2). Therefore, the value of k can be measured
through recording the concentration of the esters (B) with time (t).
Figure S1. The value of k can be measured via recording the concentration of the esters (B) with time (t).
a) b)
O O O O
R R R R
O O O H3C O O
CH3O- CH3O H3C O
HOCH3
HOCH3
O O O O
R R R R
O O O D3C O O
CD3O- CD3O
D3C O
DOCD3
DOCD3
Figure S2. Inverse isotope effect supporting H-bond involved transesterification mechanism. a) The
traditional base-catalyzed transesterification mechanism should not lead to isotope effect since no hydrogen
atom is involved in the reaction. b) The proposed H-bond involved transesterification mechanism should
lead to an inverse isotope effect as the case involving conversion of a dicoordinate COH bond to a
tricoordinate transition state.
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ln(B0/B)

a) b)
Figure S3. The values of k were measured for transesterification of ethyl benzoate in methanol. a) NaOH
(0.1 eq.) as catalyst, kH*A = 5.035 x 10-5/s, R2 = 0.9953, kD*A = 1.189 x 10-4/s, R2 = 0.9963, therefore, kH/kD
= 0.42; b) NaOMe (0.1 eq.) as catalyst, kH*A = 3.971 x 10-5/s, R2 = 0.9962, kD*A = 9.057 x 10-5/s, R2 =
0.9980, therefore, kH/kD = 0.44.
Transesterification of phenylmethyl acetate

5 NaOH in methanol
NaOH in d-methanol
4
0
0 1000 2000 3000 4000
reaction time (t/s)
a) b)
Figure S4. The values of k were measured for transesterification of phenylmethyl acetate in methanol. a)
NaOH (0.02 eq.) as catalyst, kH*A = 4.277 x 10-4/s, R2 = 0.9995, kD*A = 1.102 x 10-3/s, R2 = 0.9997,
therefore, kH/kD = 0.39; b) NaOMe (0.02 eq.) as catalyst, kH*A = 3.371 x 10-4/s, R2 = 0.9952, kD*A = 8.406
x 10-4/s, R2 = 0.9944, therefore, kH/kD = 0.40.
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Figures S5. Recorded transesterification of ethyl benzoate in methanol catalyzed by NaOH with time. *
stands for the methyl peak of the formed methyl benzoate.
Figures S6. Recorded transesterification of phenylmethyl acetate in methanol catalyzed by NaOH with time.
* stands for the methyl peak of the formed methyl acetate.
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Computational methods
Molecular geometries of all species were optimized without constraints via DFT
calculations using the B3LYP functional.2 The 6-31+G(d,p) basis set was used for C, H
and O atoms. Frequency calculations were carried out at the same level of theory to
identify the stationary points as minima (zero imaginary frequencies) or transition states
(one imaginary frequency), and to provide the thermal correction to free energies at

298.15 K. Intrinsic reaction coordinates (IRC)3 were calculated for all transition states to
confirm that the structures indeed connect two relevant minima. To take the solvent effect
into account, single-point energy calculations were performed at the level4 using 6-
311++G(d,p) basis set for all the atoms with continuum solvent model SMD5 in methanol.
The solvation- and entropy-corrected relative free energies are used to analyze the
reaction mechanism. All calculations were performed with the Gaussian 09 software
package.6
Figure S7. The possible four approaches for transesterification of ethyl acetate in methanol with hydroxide as a
catalyst. a) Process through [MeO…..H…..OMe]-, b) Process through [HO…..H…..OH]-), and (c) and (d) Process
through [MeO…..H…..OH]-. The energy values are all in kcal/mol.
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References
1. Floyd, N.; Vijayakrishnan, B.; Koeppe, J. R.; Davis, B. G. Angew. Chem. Int. Ed. 2009, 48, 7798-
7802.
2. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. (b) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H.
Chem. Phys. Lett. 1989, 157, 200. (c) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
3. (a) Fukui, K. J. Phys. Chem. 1970, 74, 4161. (b) Fukui, K. Acc. Chem. Res. 1981, 14, 363.

4. Zhao, Y.; Truhlar, D. G.; Theor. Chem. Acc. 2008,120,215.
5. Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378.
6. Frisch, M. J. In Gaussian 09, revision A.02; Gaussian, Inc., Wallingford, CT, 2009.
Cartesian coordinates and free energies for all calculated species

[MeO…..H…..OMe]-
G = -230.8599036 a.u.
O -1.89974 2.09015 1.43042
H -2.46805 3.10467 1.53166
O -3.08995 4.19558 1.59961
C -4.44179 4.01880 1.40981
H -4.73002 2.95125 1.27105
H -4.83839 4.55716 0.51294
H -5.05843 4.38645 2.26668
C -1.45089 1.92551 0.13224
H -1.66698 2.80574 -0.50815
H -1.91035 1.04713 -0.37893
H -0.35002 1.76271 0.07653
[MeO…..H…..OH]-
G = -191.6143201 a.u.
O -2.01494 1.86227 1.46947
H -1.49473 2.03812 2.26187
H -2.48158 2.81623 1.26110
O -3.04463 4.10075 1.07202
C -4.38326 4.17241 1.33977
H -5.04614 3.94761 0.45975
H -4.71164 5.18669 1.68777
H -4.73121 3.46758 2.14102
[EtO…..H…..OMe]-
G = -270.1265687 a.u.
O -1.70435 2.57110 -2.51352
H -2.49373 3.61302 -2.04734
O -3.13405 4.40369 -1.66560
C -4.28341 3.83298 -1.12849
H -4.07208 3.08767 -0.33425
H -4.91612 4.61683 -0.67326
H -4.90950 3.31317 -1.88369
C -0.59608 2.31896 -1.75442
H -0.49593 3.01715 -0.88489
H 0.36012 2.44364 -2.32954
C -0.56592 0.88184 -1.17568
H 0.34694 0.69362 -0.58400
H -1.44144 0.71665 -0.53379
H -0.61101 0.15013 -1.99339
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[EtO…..H…..OH]-
G = -230.8823468 a.u.
O -1.84705 2.52771 -2.25556
H -2.61782 3.43202 -1.42103
O -3.17004 4.15222 -0.86377
C -0.58155 2.27044 -1.81889
H -0.23345 2.98624 -1.02745

H 0.18604 2.35759 -2.63569
C -0.41076 0.84850 -1.22141
H 0.62615 0.65997 -0.89047

H -1.08321 0.72107 -0.36302
H -0.68315 0.09446 -1.97224
H -3.14304 4.93466 -1.42602
MeC(O)OEt
G = -307.5288120 a.u.
C -1.85776 0.37122 0.16603
O -1.28541 0.15062 1.21493
C -3.34453 0.24169 -0.06285
H -3.53994 -0.47796 -0.86388
H -3.82588 -0.08679 0.85818
H -3.76050 1.20350 -0.37868
O -1.22222 0.77144 -0.95897
C 0.21584 0.93366 -0.86721
H 0.65588 -0.02278 -0.56821
H 0.43499 1.66276 -0.08100
C 0.71294 1.39149 -2.22580
H 1.79944 1.52562 -2.19389
H 0.48046 0.65296 -2.99922
H 0.25723 2.34492 -2.51023
MeC(O)OMe
G = -268.2592136 a.u.
C -1.88836 0.35269 0.16382
O -1.25549 0.05545 1.15685
C -3.38277 0.21972 0.00163
H -3.61039 -0.45107 -0.83267
H -3.81374 -0.17322 0.92228
H -3.82351 1.19369 -0.23214
O -1.31698 0.85447 -0.95639
C 0.11319 1.02218 -0.91380
H 0.60505 0.06060 -0.74710
H 0.38608 1.43110 -1.88644
H 0.39267 1.71095 -0.11269
MeC(O)OH
G = -229.0124747 a.u.
C -1.88827 0.38991 0.07352
O -1.15669 0.04693 0.97827
C -3.38191 0.20345 0.02129
H -3.65229 -0.39147 -0.85659
H -3.71871 -0.29542 0.92942
H -3.87488 1.17549 -0.07808
O -1.41856 1.00802 -1.04227
H -0.45580 1.09300 -0.93669
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TSa1
G = -538.3571985 a.u.
C -1.61986 0.13532 0.05921
O -1.65068 1.06329 0.89016
C -2.88511 -0.62032 -0.33192
H -2.65520 -1.50060 -0.93660
H -3.40462 -0.92943 0.57789

H -3.53846 0.05363 -0.90334
O -0.82287 0.26222 -1.10798
C 0.37868 0.99805 -0.92200

H 0.97802 0.51343 -0.14038
H 0.14563 2.01724 -0.58520
C 1.13199 1.01185 -2.24588
H 2.06293 1.58591 -2.14850
H 1.38692 -0.00776 -2.55272
H 0.52500 1.47074 -3.03605
O -0.70471 -1.31215 0.80714
O 1.14075 -2.64210 -0.48839
H 0.45121 -2.10641 0.02329
C -0.52937 -1.19633 2.18216
H -1.16486 -1.90722 2.75334
H 0.51984 -1.39507 2.47809
H -0.78415 -0.17555 2.51846
C 0.49297 -3.22378 -1.59133
H 1.24784 -3.71756 -2.22045
H -0.24605 -3.99072 -1.29428
H -0.03303 -2.47746 -2.20860
Inta1
G = -538.3600854 a.u.
C -1.5149 0.03605 0.10718
O -1.59274 1.05244 0.85051
C -2.80721 -0.67200 -0.32443
H -2.60233 -1.56317 -0.92560
H -3.36530 -0.95987 0.57159
H -3.41603 0.02831 -0.90940
O -0.71939 0.14368 -1.10885
C 0.45147 0.92708 -0.96567
H 1.16786 0.41170 -0.30747
H 0.19919 1.88666 -0.49526
C 1.05946 1.13656 -2.34859
H 1.97311 1.74242 -2.27953
H 1.31879 0.17749 -2.81159
H 0.35124 1.65222 -3.00850
O -0.68217 -1.20876 0.84771
O 1.05075 -2.88115 -0.34324
H 0.42689 -2.24633 0.10590
C -0.63951 -1.12016 2.24544
H -1.41417 -1.74948 2.72795
H 0.34251 -1.46221 2.61190
H -0.79524 -0.07802 2.56063
C 0.49191 -3.21284 -1.59478
H 1.26745 -3.70244 -2.20007
H -0.35506 -3.91701 -1.50390
H 0.13428 -2.32337 -2.13285
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Inta2
G = -538.3588040 a.u.
C -1.75817 0.16648 -0.13951
O -1.94113 1.08622 -0.97414
C -2.88218 -0.81975 0.18377
H -2.52963 -1.63947 0.81549
H -3.27296 -1.22605 -0.75236

H -3.68589 -0.28059 0.70137
O -1.16680 0.51175 1.13452
C -0.17382 1.51225 1.04749

H 0.71096 1.14467 0.50608
H -0.55060 2.40605 0.53388
O -0.54337 -0.94156 -0.70658
O 0.64255 -2.82746 0.76690
H 0.18554 -2.14345 0.19857
C -0.10440 -0.71542 -2.01356
H 1.00295 -0.68673 -2.03483
H -0.46863 0.27073 -2.34416
C 1.14461 -2.17480 1.91115
H 2.06987 -1.60753 1.70108
H 1.38727 -2.93600 2.66611
H 0.41409 -1.47442 2.34065
H 0.11253 1.76494 2.07535
C -0.59008 -1.79501 -2.99489
H -1.68560 -1.80116 -3.03817
H -0.20563 -1.60852 -4.00955
H -0.25643 -2.79009 -2.67564
TSa2
G = -538.3569332 a.u.
C -1.91700 0.30623 -0.06522
O -2.07880 1.20631 -0.91661
C -3.01838 -0.70656 0.23453
H -2.65185 -1.52276 0.86165
H -3.38907 -1.11243 -0.70924
H -3.84061 -0.19167 0.74931
O -1.32284 0.64494 1.19316
C -0.32219 1.63999 1.10477
H 0.54574 1.26966 0.54081
H -0.69979 2.54558 0.61351
O -0.64515 -0.84985 -0.64370
O 0.52025 -2.72830 0.81639
H 0.06807 -2.03959 0.24202
C -0.20644 -0.61916 -1.94483
H 0.90180 -0.56501 -1.97101
H -0.58786 0.35926 -2.28473
C 1.03881 -2.07408 1.95044
H 1.95992 -1.50464 1.72660
H 1.29477 -2.83280 2.70395
H 0.31457 -1.37403 2.39255
H -0.01706 1.87096 2.13182
C -0.66484 -1.70882 -2.93059
H -1.76008 -1.74078 -2.97602
H -0.28263 -1.51323 -3.94468
H -0.30941 -2.69610 -2.61043
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TSb1
G = -499.1153172 a.u.
C -1.73665 0.35501 0.05244
O -1.74818 0.97348 1.12107
C -2.96020 -0.33543 -0.51779
H -2.68841 -1.05023 -1.29558
H -3.47462 -0.85744 0.29108

H -3.63604 0.42636 -0.93457
O -0.89426 0.74063 -0.99346
O -0.70999 -1.39111 0.42507

H -0.17492 -2.60107 -2.16566
O -0.50325 -3.17012 -1.46001
H -0.60041 -2.52440 -0.67404
C -0.70029 -1.72629 1.76460
H -1.39980 -2.55679 2.01962
H -0.98876 -0.85952 2.39295
C 0.33292 1.33053 -0.57556
H 0.13455 2.25135 -0.01114
H 0.84095 0.62244 0.09004
H 0.30481 -2.05347 2.11386
C 1.16207 1.61711 -1.82025
H 2.11849 2.07889 -1.54264
H 1.37215 0.69134 -2.36697
H 0.63340 2.29999 -2.49624
Intb1
G = -499.1166832 a.u.
C -1.59163 0.00843 0.16107
O -1.62289 0.88280 1.07634
C -2.92307 -0.44987 -0.45939
H -2.77603 -1.20230 -1.24064
H -3.55064 -0.87104 0.33321
H -3.43348 0.42249 -0.88333
O -0.73672 0.31841 -1.02420
O -0.89605 -1.35276 0.62263
H -0.16609 -1.51231 -2.03807
O 0.01031 -2.43279 -1.78145
H -0.24250 -2.36146 -0.83636
C -1.01549 -1.61825 1.99490
H -1.95991 -2.14285 2.24301
H -0.98170 -0.68374 2.57144
C 0.45997 1.00013 -0.69755
H 0.23719 1.79996 0.02032
H 1.17051 0.30908 -0.21479
H -0.18110 -2.26750 2.30144
C 1.06441 1.56693 -1.97895
H 1.99447 2.10886 -1.75876
H 1.29806 0.76960 -2.69500
H 0.36473 2.26063 -2.46024
Intb2
G = -499.1148689 a.u.
C -1.79481 0.01979 -0.10638
O -1.86051 0.79678 -1.09982
C -3.06978 -0.30128 0.68408
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H -2.88798 -1.03894 1.47179

H -3.81843 -0.69257 -0.01037
H -3.44615 0.62467 1.13355
O -0.80648 0.39173 0.94917
O -1.28186 -1.47358 -0.50477
H -0.13990 -1.39668 2.08062
O -0.05892 -2.33062 1.83023
H -0.46138 -2.27103 0.93321

C -0.83471 -1.62788 -1.82650
H -0.92538 -0.66168 -2.34390
H 0.23363 -1.91792 -1.82898

C -1.64757 -2.69618 -2.56896
H -1.26531 -2.84273 -3.59045
H -1.60292 -3.65830 -2.04329
H -2.69917 -2.39319 -2.63256
C 0.37818 0.95866 0.43075
H 0.14983 1.75084 -0.29333
H 0.93576 1.37622 1.27862
H 1.00776 0.20153 -0.06475
TSb2
G = -499.1138356 a.u.
C -1.85664 0.29893 -0.02215
O -1.82927 0.94210 -1.07603
C -3.13726 -0.17821 0.63339
H -2.93705 -0.96683 1.36047
H -3.80468 -0.55976 -0.14022
H -3.61668 0.67356 1.13759
O -0.89719 0.53355 0.97868
O -1.24703 -1.59292 -0.48317
H 0.01659 -1.62043 2.09846
O 0.11454 -2.44220 1.60142
H -0.38192 -2.21220 0.75044
C -0.84439 -1.72688 -1.79562
H -0.98156 -0.76843 -2.33777
H 0.24152 -1.97243 -1.87281
C -1.62641 -2.82337 -2.54818
H -1.28554 -2.91907 -3.59184
H -1.50107 -3.79358 -2.05061
H -2.69735 -2.58413 -2.55261
C 0.35687 0.98858 0.48900
H 0.24183 1.89215 -0.12050
H 0.97197 1.20186 1.36898
H 0.83323 0.20555 -0.11275
TSc1
G = -499.1102010 a.u.
C -1.89175 0.38964 0.26604
O -1.76246 0.88275 1.39546
C -3.11967 -0.40172 -0.14948
H -2.93872 -0.95168 -1.07426
H -3.37155 -1.10256 0.64744
H -3.95678 0.29710 -0.29444
O -1.36384 1.02528 -0.85666
C -0.18041 1.78379 -0.61668
H 0.49004 1.19590 0.01874
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H -0.43343 2.71090 -0.08226

C 0.46962 2.07310 -1.96241
H 1.36351 2.69583 -1.82463
H 0.77071 1.13421 -2.43705
H -0.22174 2.60548 -2.62759
O -0.65597 -1.21607 0.23544
O 1.31376 -1.55128 -1.36225
H 0.54083 -1.38789 -0.69280

H -0.40409 -1.21101 1.16795
C 0.90518 -2.53909 -2.26542
H 0.00742 -2.24746 -2.84162

H 1.71600 -2.72430 -2.98744
H 0.67321 -3.50193 -1.77223
Intc1
G = -499.1161756 a.u.
C -1.56645 0.01738 0.14841
O -1.63397 1.08916 0.84483
C -2.88283 -0.62263 -0.32908
H -2.70946 -1.55185 -0.88351
H -3.50304 -0.83462 0.54689
H -3.40535 0.08967 -0.97620
O -0.75806 0.09854 -1.10514
C 0.40904 0.88454 -0.99090
H 1.20324 0.32315 -0.46803
H 0.18760 1.78084 -0.39594
C 0.88226 1.26376 -2.39210
H 1.80301 1.86167 -2.34255
H 1.08713 0.36964 -2.99343
H 0.11418 1.85022 -2.91029
O -0.85932 -1.09845 0.95088
O 0.97251 -2.89382 0.00238
H 0.32940 -2.23347 0.36626
H -0.62426 -0.60439 1.74906
C 0.57458 -3.19169 -1.32038
H 0.25697 -2.29064 -1.86221
H 1.42976 -3.63992 -1.84447
H -0.25627 -3.91927 -1.35154
Intc2
G = -499.1153200 a.u.
C -1.36314 -0.08706 -0.12478
O -1.28135 0.93092 -0.89120
C -2.75192 -0.54234 0.35027
H -2.69847 -1.44153 0.97318
H -3.37617 -0.74594 -0.52466
H -3.19902 0.27184 0.93028
O -0.51802 0.03883 1.08341
O -0.82880 -1.42146 -0.78869
O -0.43625 -3.58375 0.83685
H -0.61022 -2.80510 0.24740
H -0.04613 0.86038 0.88565
C 0.28264 -1.23156 -1.63544
H 0.23560 -0.21373 -2.04617
H 1.22750 -1.32457 -1.06678
C 0.25896 -2.26840 -2.75885
S22
View Article Online

DOI: 10.1039/C4GC02006E
H 1.13242 -2.14916 -3.41632

H 0.26995 -3.28732 -2.35392
H -0.64910 -2.15191 -3.36179
C 0.40026 -3.15439 1.89488
H 0.19179 -3.77323 2.77953
H 1.47061 -3.27754 1.64807
H 0.22686 -2.10036 2.14414

TSc2
G = -499.1094938 a.u.
C -1.42885 0.06785 0.10022

O -0.97817 1.03466 -0.53983
C -2.82662 -0.48380 -0.13769
H -2.95224 -1.46071 0.33328
H -2.99585 -0.57316 -1.21209
H -3.55865 0.22119 0.28138
O -1.12533 -0.04281 1.46971
O -0.47428 -1.51223 -0.47066
O 0.94315 -2.69056 1.39113
H 0.40306 -2.21530 0.67686
H -0.25011 0.36309 1.55505
C 0.26047 -1.31017 -1.63225
H 0.31599 -0.22751 -1.85548
H 1.30510 -1.66108 -1.50048
C -0.33766 -2.03947 -2.85107
H 0.27092 -1.87629 -3.75464
H -0.39647 -3.11908 -2.66216
H -1.35344 -1.67683 -3.05156
C 0.03828 -3.22911 2.32223
H -0.55291 -4.06554 1.90435
H 0.60762 -3.62297 3.17719
H -0.67029 -2.47355 2.69642
S23

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