Regioselective formation of 6-O-acylsucroses and 6,3′-di-O-acylsucroses via the stannylene acetal method

Article abstract of DOI:10.1016/j.carres.2007.08.014

Regioselective formation of 6-O-acylsucroses and 6,3′-di-O-acylsucroses in one pot with good yields was achieved for the first time by a typical acylation method of sucrose via its dibutylstannylene acetal. Pure monoesters at OH-6 and diesters at OH-6,3′ obtained by these procedures were readily isolated by simple column chromatography, thus overcoming the main difficulties associated with regioselectivity, efficiency, and isolation techniques for the practical preparation. Explanations for the regioselectivities observed during this stannylene acetal-mediated reaction were also proposed based on the structures of the stannylene acetal in solution and the intramolecular migration of stannylenes.

Full text of DOI:10.1016/j.carres.2007.08.014

Available online at www.sciencedirect.com
Carbohydrate Research 342 (2007) 2657–2663
Note
Regioselective formation of 6-O-acylsucroses
and 6,30-di-O-acylsucroses via the stannylene acetal method
Qinghui Wang, Shufen Zhang* and Jinzong Yang
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, PR China
Received 24 May 2007; received in revised form 10 August 2007; accepted 15 August 2007
Available online 28 August 2007
Abstract—Regioselective formation of 6-O-acylsucroses and 6,30-di-O-acylsucroses in one pot with good yields was achieved for the
first time by a typical acylation method of sucrose via its dibutylstannylene acetal. Pure monoesters at OH-6 and diesters at OH-6,30
obtained by these procedures were readily isolated by simple column chromatography, thus overcoming the main difficulties asso-
ciated with regioselectivity, efficiency, and isolation techniques for the practical preparation. Explanations for the regioselectivities
observed during this stannylene acetal-mediated reaction were also proposed based on the structures of the stannylene acetal in solu-
tion and the intramolecular migration of stannylenes.
ꢀ 2007 Elsevier Ltd. All rights reserved.
Keywords: Sucrose; Esterification; Regioselective; Stannylene acetal
Sucrose esters synthesized from renewable resources
continue to receive widespread attention owing to their
superior performance and compatibility in the health
and environmental arenas.1 Most of the products are
used as mixtures of regioisomers as well as mono-, di-,
and triesters, with physicochemical properties depending
on the average degree of substitution and on the length
of the fatty chains. On the other hand, in order to get
some precise structure–activity relationships in this ser-
ies of compounds,2,3 it is necessary to prepare pure
sucrose fatty esters of defined structure. Many
researchers have focused their attention on the search
for regioselective reactions, since the regioselectivity is
also one source of controlling the degree of substitu-
tion.4,5 The standard procedure for the preparation of
specific sucrose esters requires suitable, partially pro-
tected sucrose derivatives, thereby necessitating a num-
ber of tedious protection and deprotection steps.
Selective acylation of unprotected sucrose has been
accomplished by enzymatic approaches,6–10 as well as
by a method introduced by Plusquellec and co-work-
ers.11–14 These methods depend on the availability of en-
zymes and the activation of the acyl component, and can
result in the monoesters at one of the primary OH-6, 60,
and 10 or the secondary OH-2.6–16 Acylation of unpro-
tected sucrose under Mitsunobu conditions5 results in
the formation of 6,60-diesters with good selectivity along
with small amounts of the 6-ester and 60-ester are ob-
tained simultaneously. However, in spite of these efforts,
to get another method giving selectively other com-
pounds remains difficult at present because of the similar
reactivity of the eight hydroxyl groups and the existence
of intramolecular migration processes. As almost all of
the selective acylations are at the primary hydroxyls
(6, 60 or 10) or the secondary OH-2, highly regioselective
synthesis of mono- or diesters at other secondary
hydroxyls is more challenging. Herein, we wish to report
a highly regioselective method for the one-pot syntheses
of 6-O-acylsucroses and simultaneous 6,30-di-O-acylsuc-
roses via dibutylstannylene acetal intermediates.
The stannylene acetal method has been widely used to
modify the reactivity of hydroxyl groups of both polyol
systems (e.g., carbohydrates) and simple glycols and to
effect their derivatization, via acylation, tosylation, and
alkylation, with high specificity under mild condi-
tions.17–21 It accomplishes primary hydroxyl activation
*
Corresponding author. Tel./fax: +86 411 8899 3621; e-mail:
zhangshf@chem.dlut.edu.cn
0008-6215/$ - see front matter ꢀ 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2007.08.014

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Q. Wang et al. / Carbohydrate Research 342 (2007) 2657–2663
Table 1. Syntheses of 6-O-acylsucrose and 6,30-di-O-acylsucrose
and temporary secondary hydroxyl protection in a sin-
gle operation and has been proven to be especially useful
in the selective acylation of sucrose. Linhardt and co-
workers demonstrated that sucrose can be acylated in
excellent yield at the 6-OH position via a dibutylstannyl-
ene intermediate.22,23 In this paper, we describe the re-
sults of our investigations on the regioselective
acylation of sucrose via a typical stannylene acetal meth-
od. Owing to this work 6,30-di-O-acylsucroses could be
obtained in a highly purified state with good yields for
the first time.
Entry
Acylation
conditionsa
Isolated yieldsb (%)
Reagent Time 6-O-Acylsucrose 6,30-Di-O-acylsucrose
(h)
1
2
3
4
5
6
2a
2b
2c
2d
2e
2f
1.5
2
2
5
8
3a: 50
3b: 45
3c: 31
3d: 29
3e: 37
3f: 37
4a: 20
4b: 21
4c: 29
4d: 26
4e: 20
4f: 15
8
a Sucrose and reagent were used in the molar ratio of 1:1; molecular
equivalent of pyridine was 1.0 to acylating reagent.
b Based on sucrose.
OR1
OH
O
6
O
HO
HO
HO
OH
O
3'
OR2
OH
chromatography, and pure compounds 3c and 4c were
obtained in isolated yields of 31% and 29% (Table 1,
entry 3), respectively.
1: R1 = R2 =H
3: R2 = H, R1 = CO-R
4: R1 = R2 = CO-R
Following the successful and unusual regioselectivity
of the reaction, we sought to determine the generality
of the system. We treated the acetal with different fatty
acid chlorides 2a–f, and the results are listed in Table
1. In all cases, good yields and high regioselectivities
were obtained. The reaction times and conditions for
all these reactions were comparable, though acyl chlo-
rides with longer fatty chains required significantly long-
er reaction times (<8 h). Since the stannylene acetal
method has been used in the regioselective acylation of
sucrose,22,23 it is somewhat surprising that the highly
regioselective formation of 6,30-di-O-acylsucroses in
these procedures has not previously been reported. Fur-
thermore, in comparison with those previously reported,
our reactions are faster and more efficient.
O
C
R
Cl
2
a: R = (CH2)6-CH3
b: R = (CH2)8-CH3
c: R = (CH2)10-CH3
d: R = (CH2)12-CH3
e: R = (CH2)14-CH3
f: R = (CH2)16-CH3
The dibutylstannylene acetal intermediate could be
prepared from sucrose (10 mmol) and dibutyltin oxide
(1.0 equiv) in methanol as solvent. The reaction was dri-
ven to completion by removal of methanol and water to
afford the required stannylene acetal. The resulting ace-
tal was allowed to react first with lauroyl chloride 2c
(1.0 equiv) in the presence of pyridine (1.0 equiv) in
anhyd DMF, resulting in a mixture containing 6-
O-acylsucrose 3c and 6,30-di-O-acylsucrose 4c (Fig. 1).
Remarkably, of the possible diacylated products, 4c
was the sole product formed with a HPLC yield of
31% based on sucrose. Simultaneously, 3c was obtained
as the sole monoacylated product in 32% yield. The mix-
ture was then subjected to further isolation by column
6-O-Acylsucroses 3a–f and 6,30-di-O-acylsucroses 4a–
f were fully characterized using ESI mass spectrometry
1
and H and 13C NMR spectroscopy. Spectral assign-
ments of 1H and 13C NMR spectra were performed
1
1
using H–1H COSY, H–13C COSY, and HMBC tech-
niques. For 6-O-acylsucroses, correlation in the HMBC
NMR spectrum between the carbonyl group and pro-
tons H-6a,b, as well as the deshielding of protons H-
6a and H-6b and of carbon C-6, ascertained the acyla-
tion position at OH-6. And for 6,30-di-O-acylsucroses,
correlation in the HMBC NMR spectrum between the
carbonyl group and proton H-30 as well as protons H-
6a,b ascertained that the acylation positions are at
OH-6 and OH-30.
Encouraged by these initial results, we subjected this
reaction to a further investigation to explore the scope
and mechanistic aspects of it. The results are listed in
Table 2. When the stannylene acetal of sucrose was trea-
ted with 0.5 equiv of lauroyl chloride, 6-O-acylsucrose
3c was obtained in a higher yield (34%), and correspond-
ingly a decreased yield of 6% was observed for 6,30-di-
O-acylsucrose 4c (entry 1). However, treatment with
2.0 equiv of lauroyl chloride resulted in a complex
Figure 1. A typical HPLC chromatograph of the crude products
(Table 1, entry 3) using an evaporative light-scattering detector
(ELSD).

Q. Wang et al. / Carbohydrate Research 342 (2007) 2657–2663
Table 2. Acylation of sucrose under various conditions: isolated yields
2659
OH
O
HO
O
in the crude products
3
HO
OH
OH
4
Isolated yieldsc (%)
O
Entry Reagent 2c
Pyridine
OH
6
(mol equiv)a (mol equiv)b
O
6,30-Di-O-
Bu
Bu
O
O
Bu
Bu
6-O-
Sn
Sn
Acylsucrose acylsucrose
O
6
4
O
OH
1
2
3
4
5
0.5
1
2
1
1
1
1
1
0.2
0
3c: 34
3c: 31
15d
3c: 31
—
4c: 6
4c: 29
45d
4c: 29
—
O
HO
HO
3
OH
O
OH
OH
Scheme 1. An idealized picture of the dimeric dibutylstannylene acetal
a Molecular equiv based on sucrose.
b Molecular equiv based on reagent 2c.
c Based on sucrose.
of sucrose.
d Mixture of several regioisomers.
both OH-6 and OH-30 were activated. There is no doubt
that stannylene acetals react much faster with electro-
philes than do free hydroxyl groups because of the good
yields and high regioselectivities we obtained.
Another explanation could be that intramolecular
migration of stannylenes leads to the activation of
OH-30. This trend may be explained as follows: initially
the acyl chloride attacks the O-6 and the chloride re-
leased from the acyl chloride leads to the intramolecular
migration of stannylene to the site (OH-30) where substi-
tution is most rapid by displacement of equilibrium. It
has been demonstrated that these universal migrations
contribute efficiently to the regiospecificity of the stann-
ylene reaction.25
In conclusion, we have introduced a convenient pro-
tocol for the regioselective synthesis of 6-O-acylsucrose
and simultaneously 6,30-di-O-acylsucrose via the dibut-
ylstannylene acetal method in a one-pot reaction. The
reactions are rapid and highly selective. It is noteworthy
that a highly regioselective synthesis of 6,30-di-O-acyl-
sucrose with excellent yields is reported herein for the
first time to the best of our knowledge. This strategy
also provides a fast and efficient approach to diversify
the pure sucrose esters of defined structures for precise
structure–activity relationship studies. Further theoreti-
cal and applied works aimed at the expansion of the
method should be pursued.
mixture of products containing mono-, di-, tri-, and
higher acylsucroses; furthermore, several different posi-
tional isomers coexisted in each of the fractions (entry
3). These results indicate that the molar ratio of acyl
chloride to sucrose is an essential factor to control the
yields and regioselectivities in the acylating reaction.
It was next important to consider the role of the
amine base pyridine in the acylating reaction. We varied
the amount of pyridine from 1.0 to 0.2 equiv (based on
lauroyl chloride), and almost no difference in yields and
regioselectivities of both 3c and 4c was obtained (entries
2 and 4). However, when the acylating reaction was con-
ducted in the absence of pyridine, only small amounts of
monoesters formed (entry 5). This suggests that in the
stannylene acetal procedure, the base is a requisite but
the amount of it is not crucial to the yield and regio-
selectivity, whereas a full 1 equiv base is required to re-
move HCl from the direct acylation of unprotected
sucrose with acyl chloride. And this is consistent with
the results of other typical acylations of stannylene ace-
tals.16 Therefore, it may be inferred that the acylations
at both OH-6 and OH-30 undergo the typical reaction
of the stannylene acetal method.
The generally accepted explanation for the regioselec-
tivities observed during stannylene acetal-mediated reac-
tions invokes dimers, trimers, and higher oligomers of
the five-coordinated tin as the reactive species.24 How-
ever, the stannylene acetals of many carbohydrates do
not undergo regioselective reactions, and neither the
types of structures of substrates for which selective reac-
tions can be anticipated, nor the cause of the selectivity
have been fully defined. The stannylene acetal of sucrose
has never been considered to exist as a dimer (Scheme 1)
in both the solid states and in solutions.22 In each of the
monomeric subunit in the dimer, there is one apical
dicoordinate oxygen (O-6) and one equatorial tricoordi-
nate oxygen (O-4). The apical oxygen is reportedly much
more reactive than the tricoordinate equatorial oxygen.
However, our result indicated that stannylene acetal of
sucrose might exist as a more complex mixture in part
of which only OH-6 was activated and in some others
1. Experimental
1.1. General methods
HPLC analyses were carried using an HP 1050 HPLC
system equipped with an Alltech 2000 evaporative
light-scattering detector (ELSD). A reversed-phase
C18-ODSA column (150 · 4.6 mm, 5 lm particle size)
purchased from Elite Analytical Instruments Co., Ltd
(Dalian, China) was used for the HPLC analysis.
Thin-layer chromatography (TLC) was performed on
E. Merck 60F254 Silica Gel plates. An n-butanol–
H3PO4–H2O solution followed by heating at 90–
100 ꢁC was used to visualize the zones on the plates.

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Q. Wang et al. / Carbohydrate Research 342 (2007) 2657–2663
The relative ratios in mixed chromatography solvents
refer to the volume/volume ratio. For column chroma-
tography, E. Merck 60G Silica Gel was used. IR spectra
were measured with a Thermo Nicolet NEXUS spec-
trometer and KBr pellets. 1H and 13C NMR spectra
were recorded at ambient temperature using a Varian
102.16 (C-20), 76.53 (C-30), 73.28 (C-40), 82.76 (C-50),
61.94 (C-60), 172.34 (C@O); ESIMS m/z 491.2
[M+Na]+, 549.0 [M+2Na+Cl]+. The NMR data
matched those previously reported.14,28
1.2.2. 6,30-Di-O-octanoylsucrose (4a). Amorphous
compound; Rf 0.69 (9:1 EtOAc–MeOH); IR (KBr)
3392 (OH) and 1740 (C@O); 1H NMR (400 MHz,
DMSO-d6): d 0.86 (m, 6H, CH3), 1.26 (m, 16H,
2(CH2)4), 1.55 (m, 4H, 2CH2b), 2.33 (dd, 4H, Ja,b
12.4, JCH2a,CH2b 6.8 Hz, CH2a), 5.17 (d, 1H, J1,2
3.6 Hz, H-1), 3.33 (t, 1H, J1,2 3.6, J2,3 9.2 Hz, H-2),
3.56 (m, 1H, H-3), 3.18 (t, 1H, J4,5 9.2 Hz, H-4), 3.15
(t, 1H, J5,4 9.2 Hz, H-5), 3.87 (d, 1H, J6a,6b 12.0 Hz,
H-6a), 4.03 (d, 1H, J6b,6a 12.0 Hz, H-6b), 3.51–3.54 (m,
1
INOVA spectrometer in DMSO-d6. H and 13C NMR
chemical shifts were assigned on the basis of 1H–1H
COSY, 1H–13C COSY, and HMBC experiments. Chem-
ical shift values are reported in d (ppm) relative to Me4Si
(using the DMSO residual peaks as reference). Coupling
constants (J) are in Hz. ESI mass spectra (ESIMS) were
measured using an HP 1100 MSD instrument. Elemen-
tal analyses were determined using a Vario EL III
instrument. All reagents were of commercial quality
and were purified according to general procedures.
2H, H-10), 5.15 (d, 1H, J3 ;4 3:6 Hz, H-30), 4.08 (t, 1H,
0
0
J3 ;4 3:6, J4 ;5 8:6 Hz, H-40), 3.71 (m, 1H, H-50), 3.54–
3.67 (m, 2H, H-60); 13C NMR (100 MHz, DMSO-d6):
d 13.97 (CH3), 22.07, 24.36, 24.48, 28.42, 31.15, 33.30,
33.52 (CH2), 91.76 (C-1), 72.94 (C-2), 73.09 (C-3),
71.10 (C-4), 69.59 (C-5), 63.92 (C-6), 60.49 (C-10),
100.92 (C-20), 76.83 (C-30), 71.10 (C-40), 82.84 (C-50),
61.61 (C-60), 172.27, 172.49 (C@O); ESIMS: m/z 617.3
[M+Na]+, 675.3 [M+2Na+Cl]+. Anal. Calcd for
C28H50O13Æ2H2O: C, 53.32; H, 8.63. Found: C, 53.39;
H, 8.45.
0
0
0
0
1.2. General procedure for acylation of sucrose
A mixture of sucrose (3.42 g, 10 mmol) and dibutyltin
oxide (2.49 g, 10 mmol) was refluxed in MeOH until
the solution became clear, after which time the solvent
was evaporated to leave the stannylene acetal as a white
crystalline solid. A solution of acetal in 30 mL of anhyd
DMF in the presence of pyridine was treated with the
appropriate acyl chloride under the conditions reported
in Tables 1 and 2 and stirred at room temperature. The
reaction’s progress was monitored by TLC using 9:1
EtOAC–MeOH. After extracting three times with
100 mL of petroleum ether in order to remove dibutyltin
by-products, the solution was concentrated in vacuo to
dryness. Acetone (100 mL) was then added to the solid
residue, and the mixture was stored at 6 ꢁC for 12 h.
The unreacted sucrose precipitated out and was filtered
off. The clear acetone solution was concentrated in
vacuo to dryness, and then the crude product was sub-
jected to HPLC analysis26,27 (0:100 to 100:0 for
100 min, flow rate of 1.0 mL/min) and isolated by col-
umn chromatography (95:5 to 90:10, EtOAC–MeOH).
The resulting products were isolated with yields as re-
ported in Tables 1 and 2.
1.2.3. 6-O-Decanoylsucrose (3b). Colorless solid; Rf
0.25 (9:1 EtOAc–MeOH); IR (KBr) 3393 (OH) and
1
1742 (C@O); H NMR (400 MHz, DMSO-d6): d 0.86
(m, 3H, CH3), 1.25 (m, 12H, (CH2)6), 1.52 (m, 2H,
CH2b), 2.31 (t, 2H, JCH2a,CH2b 7.4 Hz, CH2a), 5.18 (d,
1H, J1,2 3.2 Hz, H-1), 3.45 (m, 1H, H-2), 3.65 (m, 1H,
H-3), 3.18 (m, 1H, H-4), 3.14 (m, 1H, H-5), 3.96 (d,
1H, J6a,6b 12.2 Hz, H-6a), 4.16 (d, 1H, J6b,6a 12.2 Hz,
H-6b), 3.45–3.52 (m, 2H, H-10), 3.84 (m, 1H, H-30),
3.81 (m, 1H, H-40), 3.52 (m, 1H, H-50), 3.50–3.54 (m,
2H, H-60); 13C NMR (100 MHz, DMSO-d6): d 13.94
(CH3), 22.07, 24.45, 28.43, 28.65, 28.72, 28.84, 31.26,
33.51 (CH2), 92.07 (C-1), 72.76 (C-2), 72.90 (C-3),
71.36 (C-4), 69.79 (C-5), 62.22 (C-6), 60.45 (C-10),
102.16 (C-20), 76.54 (C-30), 73.27 (C-40), 82.76 (C-50),
61.93 (C-60), 172.35 (C@O); ESIMS: m/z 519.2
[M+Na]+, 577.3 [M+2Na+Cl]+. The NMR data
matched those previously reported.5,16
1.2.1. 6-O-Octanoylsucrose (3a). Colorless solid; Rf
0.24 (9:1 EtOAc–MeOH); IR (KBr) 3392 (OH) and
1
1740 (C@O); H NMR (400 MHz, DMSO-d6): d 0.86
(m, 3H, CH3), 1.26 (m, 8H, (CH2)4), 1.53 (m, 2H,
CH2b), 2.32 (t, 2H, JCH2a,CH2b 7.4 Hz, CH2a), 5.18 (d,
1H, J1,2 1.8 Hz, H-1), 3.47 (m, 1H, H-2), 3.65 (t, 1H,
J2,3 8.4, J4,3 8.4 Hz, H-3), 3.17 (m, 1H, H-4), 3.16 (m,
1H, H-5), 3.96 (d, 1H, J6a,6b 12.0 Hz, H-6a), 4.16 (d,
1H, J6b,6a 12.0 Hz, H-6b), 3.47–3.56 (m, 2H, H-10),
3.83 (m, 1H, H-30), 3.80 (m, 1H, H-40), 3.53 (m, 1H,
H-50), 3.50–3.54 (m, 2H, H-60); 13C NMR (100 MHz,
DMSO-d6): d 13.91 (CH3), 22.02, 24.44, 28.34, 31.08,
33.50 (CH2), 92.06 (C-1), 72.75 (C-2), 72.89 (C-3),
71.35 (C-4), 69.78 (C-5), 62.21 (C-6), 60.44 (C-10),
1.2.4. 6,30-Di-O-decanoylsucrose (4b). Amorphous
compound; Rf 0.75 (9:1 EtOAc–MeOH); IR (KBr)
3393 (OH) and 1742 (C@O); 1H NMR (400 MHz,
DMSO-d6): d 0.86 (m, 6H, CH3), 1.24 (m, 24H,
2(CH2)6), 1.53 (m, 4H, 2CH2b), 2.32 (dd, 4H, Ja,b 13.4,
JCH2a,CH2b 6.6 Hz, CH2a), 5.17 (d, 1H, J1,2 2.8 Hz, H-
1), 3.33 (t, 1H, J2,1 2.8, J2,3 9.0 Hz, H-2), 3.58 (m, 1H,
H-3), 3.17 (m, 1H, H-4), 3.15 (m, 1H, H-5), 3.87 (d,
1H, J6a,6b 11.6 Hz, H-6a), 4.02 (d, 1H, J6b,6a 11.6 Hz,
H-6b), 3.55–3.59 (m, 2H, H-10), 5.15 (d, 1H,

Q. Wang et al. / Carbohydrate Research 342 (2007) 2657–2663
2661
1
J3 ;4 3:2 Hz, H-30), 4.08 (t, 1H, J3 ;4 3:2, J4 ;5 8:4 Hz,
H-40), 3.71 (m, 1H, H-50), 3.59–3.62 (m, 2H, H-60);
13C NMR (100 MHz, DMSO-d6): d 13.87 (CH3),
22.01, 24.29, 24.39, 28.39, 28.59, 28.66, 28.80, 31.22,
33.25, 33.46 (CH2), 91.70 (C-1), 72.95 (C-2), 73.11 (C-
3), 71.06 (C-4), 69.61 (C-5), 63.91 (C-6), 60.49 (C-10),
100.89 (C-20), 76.87 (C-30), 71.06 (C-40), 82.76 (C-50),
61.52 (C-60), 172.24, 172.37 (C@O); ESIMS: m/z 673.3
[M+Na]+, 731.3 [M+2Na+Cl]+. Anal. Calcd for
C32H58O13Æ2H2O: C, 55.96; H, 9.10. Found: C, 56.04;
H, 8.99.
1741 (C@O); H NMR (400 MHz, DMSO-d6): d 0.85
(m, 3H, CH3), 1.23 (m, 20H, (CH2)10), 1.51 (m, 2H,
CH2b), 2.30 (t, 2H, JCH2a,CH2b 7.4 Hz, CH2a), 5.17 (d,
1H, J1,2 3.6 Hz, H-1), 3.45 (m, 1H, H-2), 3.65 (t, 1H,
J2,3 9.6, J4,3 9.6 Hz, H-3), 3.16 (m, 1H, H-4), 3.14 (m,
1H, H-5), 3.96 (d, 1H, J6a,6b 12.0 Hz, H-6a), 4.15 (d,
1H, J6b,6a 12.0 Hz, H-6b), 3.46–3.56 (m, 2H, H-10),
3.82 (m, 1H, H-30), 3.80 (m, 1H, H-40), 3.56 (m, 1H,
H-50), 3.51–3.54 (m, 2H, H-60); 13C NMR (100 MHz,
DMSO-d6): d 13.95 (CH3), 22.11, 24.47, 28.47, 28.73,
28.92, 29.04, 31.31, 33.52 (CH2), 92.10 (C-1), 72.77 (C-
2), 72.92 (C-3), 71.38 (C-4), 69.80 (C-5), 62.24 (C-6),
60.46 (C-10), 102.19 (C-20), 76.56 (C-30), 73.29 (C-40),
82.76 (C-50), 61.94 (C-60), 172.37 (C@O); ESIMS: m/z
575.2 [M+Na]+. The NMR data matched those previ-
ously reported.22
0
0
0
0
0
0
1.2.5. 6-O-Lauroylsucrose (3c). Colorless solid; Rf 0.25
(9:1 EtOAc–MeOH); IR (KBr) 3392 (OH) and 1740
(C@O); 1H NMR (400 MHz, DMSO-d6): d 0.79 (m,
3H, CH3), 1.18 (m, 16H, (CH2)8), 1.46 (m, 2H, CH2b),
2.25 (t, 2H, JCH2a,CH2b 7.2 Hz, CH2a), 5.11 (d, 1H, J1,2
3.2 Hz, H-1), 3.41 (m, 1H, H-2), 3.59 (t, 1H, J2,3 9.6,
J4,3 9.6 Hz, H-3), 3.11 (m, 1H, H-4), 3.09 (m, 1H, H-
5), 3.89 (d, 1H, J6a,6b 12.0 Hz, H-6a), 4.10 (d, 1H,
J6b,6a 12.0 Hz, H-6b), 3.42–3.52 (m, 2H, H-10), 3.78 (m,
1H, H-30), 3.76 (m, 1H, H-40), 3.51 (m, 1H, H-50),
3.50–3.54 (m, 2H, H-60); 13C NMR (100 MHz,
DMSO-d6): d 14.02 (CH3), 22.17, 24.52, 28.27, 28.52,
28.78, 28.81, 28.98, 29.08, 29.10, 31.37, 33.56 (CH2),
92.13 (C-1), 72.80 (C-2), 72.97 (C-3), 71.40 (C-4),
69.80 (C-5), 62.24 (C-6), 60.47 (C-10), 103.17 (C-20),
76.55 (C-30), 73.28 (C-40), 82.80 (C-50), 61.97 (C-60),
172.45 (C@O); ESIMS: m/z 547.2 [M+Na]+, 605.3
[M+2Na+Cl]+. The NMR data matched those previ-
ously reported.14,16
1.2.8. 6,30-Di-O-myristoylsucrose (4d). Colorless solid;
Rf 0.82 (9:1 EtOAc–MeOH); IR (KBr) 3393 (OH) and
1
1741 (C@O); H NMR (400 MHz, DMSO-d6): d 0.85
(m, 6H, CH3), 1.24 (m, 40H, 2(CH2)10), 1.54 (m, 4H,
2CH2b), 2.32 (dd, 4H, Ja,b 14.0, JCH2a,CH2b 6.8 Hz,
CH2a), 5.17 (d, 1H, J1,2 2.8 Hz, H-1), 3.32 (m, 1H, H-
2), 3.58 (m, 1H, H-3), 3.17 (m, 1H, H-4), 3.15 (m, 1H,
H-5), 3.88 (d, 1H, J6a,6b 12.0 Hz, H-6a), 4.02 (d, 1H,
J6b,6a 12.0 Hz, H-6b), 3.52–3.58 (m, 2H, H-10), 5.15 (d,
1H, J3 ;4 3:2 Hz, H-30), 4.09 (dd, 1H, J3 ;4 3:2,
0
0
0
0
J4 ;5 8:4 Hz, H-40), 3.71 (m, 1H, H-50), 3.56–3.62 (m,
2H, H-60); 13C NMR (100 MHz, DMSO-d6): d 13.89
(CH3), 22.07, 24.32, 24.45, 28.44, 28.71, 28.75, 28.93,
29.03, 29.07, 31.29, 33.25, 33.50 (CH2), 91.75 (C-1),
72.93 (C-2), 73.05 (C-3), 71.09 (C-4), 69.62 (C-5),
63.96 (C-6), 60.50 (C-10), 100.91 (C-20), 76.84 (C-30),
71.04 (C-40), 82.76 (C-50), 61.55 (C-60), 172.17, 172.37
(C@O); ESIMS: m/z 785.5 [M+Na]+, 843.3 [M+2Na+
Cl]+. Anal. Calcd for C40H74O13Æ1.6H2O: C, 60.67; H,
9.83. Found: C, 60.64; H, 9.75.
0
0
1.2.6. 6,30-Di-O-lauroylsucrose (4c). Amorphous com-
pound; Rf 0.78 (9:1 EtOAc–MeOH); IR (KBr) 3392
(OH) and 1740 (C@O); H NMR (400 MHz, DMSO-
1
d6): d 0.86 (m, 6H, CH3), 1.24 (m, 32H, 2(CH2)8), 1.54
(m, 4H, 2CH2b), 2.32 (dd, 4H, Ja,b 13.0, JCH2a,CH2b
7.2 Hz, CH2a), 5.17 (d, 1H, J1,2 2.8 Hz, H-1), 3.32 (m,
1H, H-2), 3.58 (m, 1H, H-3), 3.17 (m, 1H, H-4), 3.14
(m, 1H, H-5), 3.87 (d, 1H, J6a,6b 12.0 Hz, H-6a), 4.02
(d, 1H, J6b,6a 12.0 Hz, H-6b), 3.55–3.59 (m, 2H, H-10),
1.2.9. 6-O-Palmitoylsucrose (3e). Colorless solid; Rf
0.26 (9:1 EtOAc–MeOH); IR (KBr) 3402 (OH) and
1
1744 (C@O); H NMR (400 MHz, DMSO-d6): d 0.85
(m, 3H, CH3), 1.23 (m, 24H, (CH2)12), 1.52 (m, 2H,
CH2b), 2.30 (t, 2H, JCH2a,CH2b 7.2 Hz, CH2a), 5.17 (d,
1H, J1,2 3.6 Hz, H-1), 3.41 (m, 1H, H-2), 3.65 (m, 1H,
H-3), 3.18 (m, 1H, H-4), 3.15 (m, 1H, H-5), 3.96 (d,
1H, J6a,6b 12.0 Hz, H-6a), 4.16 (d, 1H, J6b,6a 12.0 Hz,
H-6b), 3.41–3.52 (m, 2H, H-10), 3.81 (m, 1H, H-30),
3.79 (m, 1H, H-40), 3.53 (m, 1H, H-50), 3.50–3.54 (m,
2H, H-60); 13C NMR (100 MHz, DMSO-d6): d 13.93
(CH3), 22.08, 24.45, 28.46, 28.70, 28.74, 28.91, 29.04,
31.28, 33.51 (CH2), 92.07 (C-1), 72.76 (C-2), 72.91 (C-
3), 71.36 (C-4), 69.79 (C-5), 62.22 (C-6), 60.45 (C-10),
102.16 (C-20), 76.54 (C-30), 73.26 (C-40), 82.74 (C-50),
61.92 (C-60), 172.33 (C@O); ESIMS: m/z 603.3
[M+Na]+. The NMR data matched those previously
reported.14,22
5.15 (d, 1H, J3 ;4 2:0 Hz, H-30), 4.08 (dd, 1H, J3 ;4 2:0,
0
0
0
0
J4 ;5 8:4 Hz, H-40), 3.71 (m, 1H, H-50), 3.59–3.62 (m,
2H, H-60); 13C NMR (100 MHz, DMSO-d6): d 13.97
(CH3), 22.15, 24.37, 24.51, 28.50, 28.79, 29.00, 29.10,
31.37, 33.30, 33.54 (CH2), 91.79 (C-1), 72.95 (C-2),
73.11 (C-3), 71.13 (C-4), 69.62 (C-5), 63.97 (C-6),
60.51 (C-10), 100.94 (C-20), 76.84 (C-30), 71.04 (C-40),
82.81 (C-50), 61.59 (C-60), 172.24, 172.45 (C@O);
ESIMS: m/z 729.5 [M+Na]+. Anal. Calcd for
C36H66O13Æ1.8H2O: C, 58.48; H, 9.49. Found: C,
58.54; H, 9.35.
0
0
1.2.7. 6-O-Myristoylsucrose (3d). Colorless solid; Rf
0.26 (9:1 EtOAc–MeOH); IR (KBr) 3393 (OH) and

2662
Q. Wang et al. / Carbohydrate Research 342 (2007) 2657–2663
1.2.10. 6,30-Di-O-palmitoylsucrose (4e). Amorphous
compound; Rf 0.85 (9:1 EtOAc–MeOH); IR (KBr)
3402 (OH) and 1744 (C@O); 1H NMR (400 MHz,
DMSO-d6): d 0.85 (m, 6H, CH3), 1.24 (m, 48H,
2(CH2)12), 1.54 (m, 4H, 2CH2b), 2.32 (m, 4H, CH2a),
5.17 (d, 1H, J1,2 2.8 Hz, H-1), 3.32 (m, 1H, H-2), 3.58
(m, 1H, H-3), 3.17 (m, 1H, H-4), 3.15 (m, 1H, H-5),
3.88 (d, 1H, J6a,6b 12.0 Hz, H-6a), 4.01 (d, 1H, J6b,6a
12.0 Hz, H-6b), 3.52–3.58 (m, 2H, H-10), 5.15 (d, 1H,
Anal. Calcd for C48H90O13Æ1.8H2O: C, 63.52; H, 10.39.
Found: C, 63.51; H, 10.24.
Acknowledgments
We gratefully acknowledge financial support from the
National Natural Science Funds for Distinguished
Young Scholar of China (Grant No. 20525620) and
the Natural Science Foundation of Liaoning province,
China (Grant No. 20042158).
J3 ;4 3:2 Hz, H-30), 4.09 (m, 1H, H-40), 3.71 (m, 1H,
H-50), 3.56–3.62 (m, 2H, H-60); 13C NMR (100 MHz,
DMSO-d6): d 13.88 (CH3), 22.06, 24.30, 24.45, 25.51,
28.40, 28.69, 29.05, 31.27, 33.23, 33.49 (CH2), 91.73
(C-1), 72.92 (C-2), 73.04 (C-3), 71.09 (C-4), 69.60 (C-
5), 63.96 (C-6), 60.48 (C-10), 100.90 (C-20), 76.82 (C-
30), 71.04 (C-40), 82.75 (C-50), 61.55 (C-60), 172.17,
172.36 (C@O); ESIMS: m/z 853.6 [M+Cl]ꢀ. Anal. Calcd
for C44H82O13Æ1.9H2O: C, 61.93; H, 10.13. Found: C,
61.95; H, 9.91.
0
0
References
1. Devulapalle, K. S.; Segura, A. G.; Ferrer, M.; Alcalde, M.;
Mooser, G.; Plou, F. J. Carbohydr. Res. 2004, 339, 1029–
1034.
2. Molinier, V.; Kouwer, P. J. J.; Fitremann, J.; Bouchu, A.;
Mackenzie, G.; Queneau, Y.; Goodby, J. W. Chem. Eur. J.
2006, 12, 3547–3557.
1.2.11. 6-O-Stearoylsucrose (3f). Colorless solid; Rf
3. Molinier, V.; Kouwer, P. J. J.; Fitremann, J.; Bouchu, A.;
Mackenzie, G.; Queneau, Y.; Goodby, J. W. Chem. Eur. J.
2007, 13, 1763–1775.
4. Queneau, Y.; Fitremann, J.; Trombotto, S. C.R. Chim.
2004, 7, 177–188.
5. Molinier, V.; Fitremann, J.; Bouchu, A.; Queneau, Y.
Tetrahedron: Asymmetry 2004, 15, 1753–1762.
6. Riva, S.; Chopineau, J.; Kieboom, A. P. G.; Klibanov, A.
J. Am. Chem. Soc. 1988, 110, 584–589.
7. Ferrer, M.; Cruces, M. A.; Bernabe, M.; Ballesteros, A.;
Plou, F. J. Biotechnol. Bioeng. 1999, 65, 10–15.
8. Potier, P.; Bouchu, A.; Descotes, G.; Queneau, Y.
Tetrahedron Lett. 2000, 41, 3597–3600.
9. Potier, P.; Bouchu, A.; Gagnaire, J.; Queneau, Y. Tetra-
hedron: Asymmetry 2001, 12, 2409–2419.
10. Potier, P.; Bouchu, A.; Descotes, G.; Queneau, Y.
Synthesis 2001, 3, 458–462.
11. Baczko, K.; Plusquellec, D. Tetrahedron 1991, 47, 3817–
3828.
12. Chauvin, C.; Baczko, K.; Plusquellec, D. J. Org. Chem.
1993, 58, 2291–2295.
0.28 (9:1 EtOAc–MeOH); IR (KBr) 3400 (OH) and
1740 (C@O); H NMR (400 MHz, DMSO-d6): d 0.87
1
(m, 3H, CH3), 1.24 (m, 28H, (CH2)14), 1.53 (m, 2H,
CH2b), 2.31 (t, 2H, JCH2a,CH2b 6.6 Hz, CH2a), 5.18 (d,
1H, J1,2 3.6 Hz, H-1), 3.41 (m, 1H, H-2), 3.65 (m, 1H,
H-3), 3.18 (m, 1H, H-4), 3.15 (m, 1H, H-5), 3.96 (d,
1H, J6a,6b 12.0 Hz, H-6a), 4.16 (d, 1H, J6b,6a 12.0 Hz,
H-6b), 3.41–3.52 (m, 2H, H-10), 3.81 (m, 1H, H-30),
3.79 (m, 1H, H-40), 3.53 (m, 1H, H-50), 3.50–3.54 (m,
2H, H-60); 13C NMR (100 MHz, DMSO-d6): d 13.91
(CH3), 22.10, 24.46, 28.48, 28.73, 28.77, 28.94, 29.07,
31.31, 33.51 (CH2), 92.10 (C-1), 72.77 (C-2), 72.93 (C-
3), 71.38 (C-4), 69.81 (C-5), 62.23 (C-6), 60.48 (C-10),
102.17 (C-20), 76.57 (C-30), 73.25 (C-40), 82.74 (C-50),
61.89 (C-60), 172.32 (C@O); ESIMS: m/z 643.5
[M+Cl]ꢀ. The NMR data matched those previously
reported.14,22
13. Chauvin, C.; Plusquellec, D. Tetrahedron Lett. 1991, 32,
3495–3498.
1.2.12. 6,30-Di-O-stearoylsucrose (4f). Colorless solid;
Rf 0.88 (9:1 EtOAc–MeOH); IR (KBr) 3400 (OH) and
1740 (C@O); H NMR (400 MHz, DMSO-d6): d 0.85
14. Baczko, K.; Chauvin, C.; Banoub, J.; Thibault, P.;
Plusquellec, D. Carbohydr. Res. 1995, 269, 79–88.
15. Teranishi, K. Carbohydr. Res. 2002, 337, 613–619.
16. Molinier, V.; Wisniewski, K.; Bouchu, A.; Fitremann, J.;
Queneau, Y. J. Carbohydr. Chem. 2003, 22, 657–669.
17. David, S.; Hanessian, S. Tetrahedron 1985, 41, 643–663.
18. Leigh, D. A.; Martin, R. P.; Smart, J. P.; Truscello, A. M.
J. Chem. Soc., Chem. Commun. 1994, 1373–1374.
19. Martinelli, M. J.; Nayyar, N. K.; Moher, E. D.; Dhokte,
U. P.; Pawlak, J. M.; Vaidyanathan, R. Org. Lett. 1999, 1,
447–450.
20. Martinelli, M. J.; Vaidyanathan, R.; Khau, V. V. Tetra-
hedron Lett. 2000, 41, 3773–3776.
21. Martinelli, M. J.; Vaidyanathan, R.; Pawlak, J. M.;
Nayyar, N. K.; Dhokte, U. P.; Doecke, C. W.; Zollars,
L. M. H.; Moher, E. D.; Khau, V. V.; Kosmrlj, B. J. Am.
Chem. Soc. 2002, 124, 3578–3585.
1
(m, 6H, CH3), 1.23 (m, 56H, 2(CH2)14), 1.54 (m, 4H,
2CH2b), 2.32 (m, 4H, CH2a), 5.17 (d, 1H, J1,2 2.4 Hz,
H-1), 3.32 (m, 1H, H-2), 3.58 (m, 1H, H-3), 3.18 (m,
1H, H-4), 3.16 (m, 1H, H-5), 3.89 (d, 1H, J6a,6b
11.8 Hz, H-6a), 4.01 (d, 1H, J6b,6a 11.8 Hz, H-6b),
3.52–3.58 (m, 2H, H-10), 5.15 (d, 1H, J3 ;4 1:6 Hz, H-
0
0
30), 4.09 (dd, 1H, J3 ;4 1:6, J4 ;5 6:4 Hz, H-40), 3.71
(m, 1H, H-50), 3.56–3.62 (m, 2H, H-60); 13C NMR
(100 MHz, DMSO-d6): d 13.88 (CH3), 22.07, 24.30,
24.46, 28.44, 28.71, 28.78, 29.07, 31.29, 33.22, 33.50
(CH2), 91.75 (C-1), 72.92 (C-2), 73.05 (C-3), 71.10 (C-
4), 69.61 (C-5), 63.98 (C-6), 60.50 (C-10), 100.92 (C-20),
76.83 (C-30), 71.03 (C-40), 82.74 (C-50), 61.56 (C-60),
172.16, 172.35 (C@O); ESIMS: m/z 909.5 [M+Cl]ꢀ.
0
0
0
0
22. Vlahov, I. R.; Vlahova, P. I.; Linhardt, R. J. J. Carbohydr.
Chem. 1997, 16, 1–10.

Q. Wang et al. / Carbohydrate Research 342 (2007) 2657–2663
2663
23. Bazin, H. G.; Polat, T.; Linhardt, R. J. Carbohydr. Res.
1998, 309, 189–205.
24. Leigh, D. A.; Martin, R. P.; Smart, J. P.; Truscello, A. M.
J. Chem. Soc., Chem. Commun. 1994, 1373–1374.
25. David, S.; Malleron, A. Carbohydr. Res. 2000, 329, 215–
218.
26. Wang, Q.; Zhang, S.; Zhang, P.; Zhu, J.; Yang, J. J. Liq.
Chromatogr. Related Technol. 2006, 29, 2399–2412.
27. Wang, Q.; Zhang, S.; Yang, J. J. Liq. Chromatogr. Related
Technol. 2007, 30, 2395–2407.
28. Thevenet, S.; Wernicke, A.; Belniak, S.; Descotes, G.;
Bouchu, A.; Queneau, Y. Carbohydr. Res. 1999, 318, 52–66.