Transition-metal-free synthesis of aryl 1-thioglycosides with arynes at room temperature

Article abstract of DOI:10.1039/d1ra04013h

A mild, convenient and transition-metal-free protocol for the synthesis of aryl 1-thioglycosides is presentedviaarynes generatedin situcombined with glycosyl thiols in the presence of TBAF(tBuOH)₄. The methodology provides a general and efficient way to prepare a series of functionalized thioglycosides in good to excellent yields with a perfect control of the anomeric configuration at room temperature. In addition, the reaction conditions tolerate a variety of the pentoses and hexoses, and the reaction also performs smoothly on protected monosaccharides and disaccharides.

Full text of DOI:10.1039/d1ra04013h

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Transition-metal-free synthesis of aryl 1-
thioglycosides with arynes at room temperature†
Cite this: RSC Adv., 2021, 11, 26666
a
a
a
a
b
*
Yao Liu,‡ Xiao-Bing Yu,‡ Xiang-Mei Zhang, Qian Zhong, Li-Hua Liao
ab
*
and Nan Yan
A mild, convenient and transition-metal-free protocol for the synthesis of aryl 1-thioglycosides is presented
via arynes generated in situ combined with glycosyl thiols in the presence of TBAF(tBuOH)4. The
methodology provides a general and efficient way to prepare a series of functionalized thioglycosides in
good to excellent yields with a perfect control of the anomeric configuration at room temperature. In
addition, the reaction conditions tolerate a variety of the pentoses and hexoses, and the reaction also
performs smoothly on protected monosaccharides and disaccharides.
Received 23rd May 2021
Accepted 22nd July 2021
DOI: 10.1039/d1ra04013h
rsc.li/rsc-advances
via the Buchwald–Hartwlg–Migita coupling reaction. These
Introduction
methods required an expensive catalyst or a high temperature
ꢀ
(above 100 C in some protocols of the Cu or Pd catalyst) and
long reaction time, which limit the universality of the reaction
to some extent. In 2019, Messaoudi and co-workers developed
a protocol for the synthesis of aryl 1-thioglycosides via a Ni/
photoredox dual catalyzed cross-coupling reaction16 (Scheme
1c). Recently, Messaoudi's group described the rst electro-
chemical method for coupling various anomeric glycosyl thiols
with aryl bromides17 (Scheme 1c). The reaction didn't need to
perform in a strong base environment, and demonstrated
superiority to synthesize highly complex thioglycosides under
mild conditions. However, some functional groups are not
compatible with this procedure.
Thioglycosides, as the analogue of the O-glycosides, are versatile
intermediates in carbohydrate synthesis and have a wide range
of potential applications,1 and are regularly used as glycosyl
donors2 to construct various oligosaccharides and glyco-
conjugates. Additionally, they are more stable in both chemical
and enzymatic degradations3 and have also been employed
extensively as inhibitors in a great number of biochemical
studies.4 Thioglycoside fragments are also widely used in
various drugs, natural products and pharmaceutical active
agents.5 Some examples of the thioglycosides derivatives
include the cytotoxic Hsp90 inhibitor,6 MUS-CB,7 hSGLT1
inhibitor,8 lincomycin,9 clindamycin,10 as well as irreversible
glycoside inhibitors11 (Fig. 1). On account of the great signi-
cance of S-glycosides, some elegant synthetic protocols have
been developed.
Originally, the approaches to prepare the 1-thioglycosides
were that glycosyl donors reacted with sulfurs (or thiophenols)
in the presence of the stoichiometric Lewis acids12 or glycosyl
halides reacted with thiolate anions under strong base condi-
tions (Scheme 1a). However, the inferior stereo-selectivity or
strong base of those traditional methods limited their applica-
tion. With the efforts of Sticha, Xue, Messaoudi et al., the
synthesis of 1-thioglycosides achieved great advances in recent
years. As shown in Scheme 1b, the functionalization of glycosyl
thiols had been catalysed by the Ni,13 Cu14, Pd15 transition metal
Arynes are highly reactive transient intermediates and are also
useful synthons in organic synthesis due to the unique triple
bonds, and have been extensively used in the synthesis of natural
products, drug molecules and functional materials.18 Arynes have
made remarkable achievements in nucleophilic reactions,19
pericyclic reactions,20 transition metal catalyzed reactions21 and
multicomponent reactions.22 In recent years, N-arylation of
carbohydrate amines23 and O-arylation of carbohydrates24 have
been reported via the aryne insertion reactions with glycosyl
aNational Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal
University, Nanchang, 330022, P. R. China. E-mail: yannan@jxnu.edu.cn
bCollege of Chemistry and Chemical Engineering, Jiangxi Normal University,
Nanchang 330022, P. R. China. E-mail: liaolihua@jxnu.edu.cn
† Electronic supplementary information (ESI) available: Additional experimental
details and complete NMR spectral data for all synthesized compounds. See
DOI: 10.1039/d1ra04013h
Fig. 1 Examples of biologically active thioglycosides.
‡ These authors contribute equally.
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(trimethylsilyl)aryl triates 2a (1.0 equiv.) as model substrate.
Phenyl-2,3,4,6-tetra-O-acetyl-1-thio-b-D-glucopyranoside 3a was
isolated aer 2 hours in 64% yield at room temperature
(entry 1, Table 1). When the equivalent of aryne precursor
increased to 1.1 equiv., the yield of desired product increased to
70% (entry 1, Table 1). In spired by this result, other uorides,
such as AgF, ZnF2, KF, more widely used tetrabutyl ammonium
uoride (TBAF) and its analogs (entries 2–7, Table 1) were
tested. To our delight, the yield of 3a increased to 86% when
TBAF$(tBuOH)4 (ref. 26) was used as a uorine source (entry 7,
Table 1). Next, we also investigated the solvent effect by using
varies polar solvents and non-polar solvents (entries 8–13, Table
1). Nucleophilic solvents such as tetrahydrofuran, methanol,
N,N-dimethylformamide and dimethyl sulfoxide exhibited low
yields (26–40%), probably because the competitive reaction
between nucleophilic solvents and the substrates. The yield of
3a was decreased to 60% when the temperature increased to
Scheme 1 Methods for the synthesis of S-glycosides.
ꢀ
60 C (entry 15). We found that the yield of the target product
was not inuenced with extended reaction time.
thiols. The methodology of using the aryne generated in situ to
realize the functionalized thioglycosides was not developed yet.
On the basis of our previous research in carbohydrates,25 we
report a novel protocol for the preparation of thioglycosides via
a tandem intermolecular nucleophilic coupling of glycosyl thiols
with arynes (Scheme 1c).
With the optimized condition in hand, the scopes of the
glycosyl thiols were further investigated and the results are
presented in Scheme 2. Various acetyl-protected b-glycosyl
thiols 1c, 1d reacted with arynes under the standard conditions
and the corresponding b-conguration thioglycosides products
(3c, 3d) were obtained in good yields (85%, 75%). This conver-
sion was also applicable for the a-conguration glycosyl thiol
substrate 1b and 1e, providing corresponding arylthioglycoside
products 3b and 3e in 80% and 77% yield, respectively. More-
over, triacetyl protected-pentose glycosyl thiols 1f, 1g partici-
pated in this reaction smoothly and the yields of the
corresponding thioglycoside products were 82% and 81%,
respectively. The reaction was not limited to monosaccharides
but also extended to disaccharides. Acetyl-protected cellobiose
1h and benzoyl-protected cellobiose 1i were reacted with arynes
Results and discussion
We started by optimizing the reaction conditions with tetra-O-
acetylated 1-thio-b-D-glucopyranose 1a (1.0 equiv.), o-
Table 1 Optimization conditions for the synthesis of S-glycosidesa
Entry
Fꢁ sources
Solvent
Time/h
T/ꢀC
Yield (%)
1
2
3
4
5
6
7
8
CsF
AgF
KF
ZnF2
TBAF$3H2O
TBAF(THF)
TBAF$(tBuOH)4
TBAF$(tBuOH)4
TBAF$(tBuOH)4
TBAF$(tBuOH)4
TBAF$(tBuOH)4
TBAF$(tBuOH)4
TBAF$(tBuOH)4
TBAF$(tBuOH)4
TBAF$(tBuOH)4
TBAF$(tBuOH)4
TBAF$(tBuOH)4
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
DCM
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
3.0
4.0
25
25
25
25
25
25
25
25
25
25
25
25
25
40
60
25
25
70(64b)
51
42
35
63
67
86
78
40
33
37
26
30
9
THF
10
11
12
13
14
15
16
17
Toluene
MeOH
DMSO
DMF
CH3CN
CH3CN
CH3CN
CH3CN
85
60
83c
82
a
Standard conditions: 1a (0.1 mmol, 1.0 equiv.), 2a (0.11 mmol, 1.1
equiv.), TBAF$(tBuOH)4 (0.2 mmol, 2.0 equiv.), CH3CN (1.5 mL) as
b
solvent, r.t., 2 h. 1a (0.1 mmol, 1.0 equiv.), 2a (0.1 mmol, 1.0 equiv.),
Fꢁ source (0.2 mmol, 2.0 equiv.), CH3CN (1.5 mL). 1a (0.1 mmol, 1.0
c
Scheme 2 Scopes of glycosyl thiols 1 reacted with aryne 2a. Standard
conditions: 1 (0.1 mmol, 1.0 equiv.), 2a (0.11 mmol, 1.1 equiv.),
TBAF$(tBuOH)4 (0.2 mmol, 2.0 equiv.), dry CH3CN (1.5 mL).
equiv.), 2a (0.11 mmol, 1.1 equiv.), TBAF$(tBuOH)4 (0.3 mmol, 3.0
equiv.), CH3CN (1.5 mL) as solvent, r.t., 2 h.
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successfully and obtained the b-disaccharide in good yields,
indicated the electronic-effect of the protecting groups did not
have signicant inuence for the reaction efficiency. Mean-
while, we also found the a-glycosyl thiols with OBn protected
group can reacted with 2a when the temperature improved to
ꢀ
45 C and the yield of corresponding product 3j was 78%. The
sugar 1k with OPiv group provided 3k in 71% yield under optical
condition. However, the reactivity of unprotected glycosyl thiol
was decreased and the yield of product was only 30%.
Subsequently, we also investigated the electronic effects and
regioselectivity of this reaction via different aryne precursors
and glycosyl thiols 1. Regardless of the electron-donating or
-withdrawing properties of the symmetrical aryne precursors 2,
the corresponding products were obtained in good yields. The
diuoro substituted aryne 2b reacted with 1 gave the thio-
glycosides derivatives 4a–4h in 71–82% yields. Aryne precursor
2c reacted with a series of glycosyl thiols under standard reac-
tion condition to afford the corresponding products 4i–4l in
good yields (72–84%). Also, the dimethyl substituted aryne
precursors reacted with 1a under standard condition to give
corresponding aryl 1-thioglycoside 4m with 78% yield.
Meanwhile, 3-methoxy non-symmetric aryne precursor 2d
exhibited excellent regioselectivity due to the steric effect and
electronic effects, and single target thio-glycosides 4n, 4o were
obtained in good yields (80%, 78%). However, we found that 4-
methylbenzyne precursor 2e reacted with 1a and 1f gave a near
equimolar mixture of two inseparable regioisomers, providing
Scheme 4 Gram-scale reaction and plausible mechanism.
corresponding products in 82% and 90% yield, respectively. 1,2-
Naphthyne precursor 2f under the same conditions also
provided
a near equimolar mixture of two inseparable
regioisomers (Scheme 3).
To demonstrate the synthetic utility of this transformation,
we next performed a scale-up reaction of 3a. As shown in
Scheme 4a, a gram scale reaction of 1-thio-b-D-glucopyranose 1a
with aryne precursor 2a proceeded to give 3a in 85% yield. A
plausible mechanism was proposed in Scheme 4b, based on the
basis of the experimental results and the related report by Jin
and co-workers.27
Conclusions
In conclusion, we have developed a convenient method for the
preparation of aryl-thioglycosides under mild and metal-
catalyst-free conditions via a tandem intermolecular nucleo-
philic coupling of glycosyl thiols with arynes. Meanwhile, the
method is applicable for various monosaccharide and disac-
charide substrates, which has wide practical value between
biochemistry and medicinal chemistry. In addition, 1,2-trans-
thioglycosides were stereoselectively formed by the reaction of
the in situ generated arynes with glycosyl thiols in good to
excellent yields. Importantly, we provided a new protocol for the
synthesis of functionalized thioglycosides and the possibility
for further derivatization of glycosyl donors.
Experimental
General information
All reactions were carried out in dried glassware. The solvent in
˚
the reaction were dried use activated 4 A molecular sieve,
commercial reagents were used without further purication
unless otherwise stated. Purication of reaction products were
carried out by ash chromatography on silica gel
(200–300 mesh). NMR spectra were measured in CDCl3 (with
TMS as internal standard) on a Bruker AV400 (1H at 400 MHz,
13C at 100 MHz, 19F at 376 MHz) magnetic resonance
spectrometer.
Scheme 3 Scope of aryne precursors 2 reacted with glycosyl thiol.
Standard condition: 1 (0.1 mmol, 1.0 equiv.), 2 (0.11 mmol, 1.1 equiv.),
TBAF$(tBuOH)4 (0.2 mmol, 2.0 equiv.), dry CH3CN (1.5 mL).
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1H), 4.20–4.09 (m, 2H), 3.95 (td, J ¼ 5.8, 2.9 Hz, 1H), 2.11 (s, 3H),
2.09 (s, 3H), 2.06 (s, 3H), 1.96 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 169.4, 169.1, 168.9, 168.3, 149.6 (dd, J ¼ 250.8, 12.5 Hz), 148.9
(dd, J ¼ 250.9, 13.0 Hz), 128.5 (dd, J ¼ 6.2, 3.7 Hz), 127.1 (dd, J ¼
6.1, 4.2 Hz), 121.1 (d, J ¼ 18.3 Hz), 116.4 (d, J ¼ 17.7 Hz), 84.9,
73.6, 70.8, 66.2, 65.9, 60.8, 19.8, 19.6, 19.5, 19.5; 19F {1H} NMR
(376 MHz, CDCl3) d ꢁ135.92 (dt, J ¼ 19.8, 9.3 Hz), ꢁ137.16 (m);
19F NMR (376 MHz, CDCl3) d ꢁ135.92 (d, J ¼ 21.0 Hz), ꢁ137.17
(d, J ¼ 20.9 Hz). HRMS (ESI): m/z calcd for C20H22F2O9SNa+ (M +
Na)+ 499.0845, found 499.0841.
The general procedure for the reaction of glycosyl thiols 1 with
aryne precursors 2
The glycosyl thiol 1 (50 mg, 0.14 mmol, 1.0 equiv.), aryne
precursor 2 (45 mg, 0.150 mmol, 1.1 equiv.) and TBAF$(tBuOH)4
(0.274 mmol, 2.0 equiv.) were sequentially added in a clean and
dry Schlenk tube, and the tube was then evacuated and back-
lled with nitrogen (this sequence was repeated three times).
Under nitrogen atmosphere, MeCN (1.5 mL) was added to the
mixture system, then the mixture was stirred at room temper-
ature for 2.0 hours. Saturated NaCl solution was added to dilute
the system and extracted with EtOAc (3 ꢂ 2 mL). The combined
organic phase was dried over anhydrous Na2SO4, ltered, and
evaporated in vacuo. Finally, the crude product was puried via
ash column chromatography on silica gel to give the desired
product.
3,4-Diuorphenyl-2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-b-
D-glucopyranoside (4d)
Puried by ash column chromatography Rf ¼ 0.28 (petroleum
ether/AcOEt
¼
1 : 2), white solid (33.6 mg, 71% yield);
[a]2D5 ¼ ꢁ24.5 (c ¼ 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) d 7.43
(ddd, J ¼ 10.0, 7.4, 2.1 Hz, 1H), 7.25–7.19 (m, 1H), 7.09 (dt, J ¼
10.1, 8.4 Hz, 1H), 5.76 (d, J ¼ 9.1 Hz, 1H), 5.19 (t, J ¼ 9.8 Hz, 1H),
5.02 (t, J ¼ 9.7 Hz, 1H), 4.77 (d, J ¼ 10.4 Hz, 1H), 4.21–4.13 (m,
2H), 4.00 (q, J ¼ 9.8 Hz, 1H), 3.77–3.67 (m, 1H), 2.08 (s, 3H), 2.02
(s, 6H), 1.98 (s, 3H); 13C NMR (100 MHz, CDCl3) d 171.0, 170.6,
170.1, 169.3, 150.6 (dd, J ¼ 251.0, 12.6 Hz), 149.9 (dd, J ¼ 250.9,
12.8 Hz), 129.6 (dd, J ¼ 6.3, 3.6 Hz), 128.2 (dd, J ¼ 6.3, 4.2 Hz),
122.1 (d, J ¼ 18.2 Hz), 117.5 (d, J ¼ 17.5 Hz), 86.4, 75.9, 73.5,
68.2, 62.3, 53.2, 23.3, 20.6, 20.6, 20.5; 19F {1H} NMR (376 MHz,
CDCl3) d ꢁ135.93 (dt, J ¼ 19.9, 9.3 Hz), ꢁ137.28 (m); 19F NMR
(376 MHz, CDCl3) d ꢁ135.93 (d, J ¼ 21.4 Hz), ꢁ137.29
(d, J ¼ 21.0 Hz). HRMS (ESI): m/z calcd for C20H23F2NO8SNa+ (M
+ Na)+ 498.1005, found 498.1006.
Phenyl-2,3,5-tri-O-acetyl-1-thio-b-D-xylofuranoside (3g)
Puried by ash column chromatography Rf ¼ 0.39 (petroleum
ether/AcOEt
¼
3 : 1), white solid (29.8 mg, 81% yield);
[a]2D5 ¼ ꢁ55.4 (c ¼ 1.0, CHCl3); 1H NMR (400 MHz, CDCl3)
d 7.55–7.46 (m, 2H, ArH), 7.40–7.28 (m, 3H, ArH), 5.18 (t, J ¼
8.2 Hz, 1H), 5.06–4.87 (m, 2H), 4.80 (d, J ¼ 8.4 Hz, 1H), 4.28 (dd,
J ¼ 11.8, 4.9 Hz, 1H), 3.42 (dd, J ¼ 11.8, 8.7 Hz, 1H), 2.09 (s, 3H),
2.05 (s, 3H), 2.04 (s, 3H); 13C NMR (100 MHz, CDCl3) d 169.9,
169.8, 169.3, 132.7, 132.2, 129.1, 128.3, 86.2, 71.9, 69.8, 68.4,
65.2, 20.8, 20.8, 20.7; HRMS (ESI) m/z calcd for C17H20O7SNa+
(M + Na)+ 391.0822, found 391.0822.
3,4-Diuorphenyl-2,3,4,6-tetra-O-acetyl-1-thio-b-D-gluco-pyranoside
(4a)
3,4-Diuorphenyl-2,3,4-tri-O-acetyl-1-thio-a-L-rhamno-pyranoside
(4e)
Puried by ash column chromatography Rf ¼ 0.30 (petroleum
ether/AcOEt
¼
3 : 1), white solid (39.1 mg, 82% yield);
Puried by ash column chromatography Rf ¼ 0.47 (petroleum
[a]2D5 ¼ ꢁ20.7 (c ¼ 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) d 7.42
(ddd, J ¼ 10.2, 7.5, 2.2 Hz, 1H), 7.24–7.19 (m, 1H), 7.10
(dt, J ¼ 10.0, 8.3 Hz, 1H), 5.21 (t, J ¼ 9.4 Hz, 1H), 5.00
(t, J ¼ 9.8 Hz, 1H), 4.90 (t, J ¼ 9.6 Hz, 1H), 4.63 (d, J ¼ 10.0 Hz,
1H), 4.19 (d, J ¼ 3.8 Hz, 2H), 3.73 (dt, J ¼ 10.1, 3.8 Hz, 1H), 2.09
(s, 3H), 2.08 (s, 3H), 2.01 (s, 3H), 1.98 (s, 3H); 19F {1H} NMR (376
MHz, CDCl3) d ꢁ135.81 (dt, J ¼ 19.7, 9.3 Hz), ꢁ136.61 (m); 19F
NMR (376 MHz, CDCl3) d ꢁ135.81 (d, J ¼ 20.9 Hz), ꢁ136.61 (d, J
¼ 21.0 Hz). 13C NMR (100 MHz, CDCl3) d 170.6, 170.1, 169.3,
169.2, 150.9 (dd, J ¼ 251.0, 12.3 Hz), 149.9 (dd, J ¼ 251.1, 12.5
Hz), 130.3 (dd, J ¼ 6.4, 3.6 Hz), 127.1 (dd, J ¼ 6.2, 4.2 Hz), 122.9
(d, J ¼ 18.2 Hz), 117.5 (d, J ¼ 17.6 Hz), 85.1, 75.9, 73.8, 69.6, 68.0,
62.0, 20.7, 20.6, 20.5; HRMS (ESI): m/z calcd for C20H22F2O9SNa+
(M + Na)+ 499.0845, found 499.0843.
ether/AcOEt
¼
3 : 1), white solid (31.8 mg, 76% yield);
[a]2D5 ¼ ꢁ116.0 (c ¼ 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) d 7.31
(ddd, J ¼ 10.0, 7.3, 2.2 Hz, 1H), 7.21–7.17 (m, 1H), 7.11 (dt, J ¼
10.0, 8.3 Hz, 1H), 5.45 (dd, J ¼ 3.3, 1.7 Hz, 1H), 5.35 (d, J ¼ 1.6 Hz,
1H), 5.21 (dd, J ¼ 10.1, 3.2 Hz, 1H), 5.14 (t, J ¼ 9.8 Hz, 1H), 4.34–
4.26 (m, 1H), 2.14 (s, 3H), 2.07 (s, 3H), 2.01 (s, 3H), 1.25 (d, J ¼
6.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) d 170.1, 170.0, 170.4,
150.5 (dd, J ¼ 250.5, 12.6 Hz), 150.3 (dd, J ¼ 251.8, 13.1 Hz), 129.4
(dd, J ¼ 6.1, 4.1 Hz), 128.6 (dd, J ¼ 6.3, 3.7 Hz), 121.2 (d, J ¼ 18.2
Hz), 118.0 (d, J ¼ 17.7 Hz), 86.0, 71.1, 71.0, 69.4, 68.1, 21.0, 20.9,
20.8, 17.4; 19F {1H} NMR (376 MHz, CDCl3) d ꢁ135.57 (dt, J ¼
20.9, 9.2 Hz), ꢁ137.48 (m); 19F NMR (376 MHz, CDCl3) d ꢁ135.57
(d, J ¼ 20.9 Hz), ꢁ137.50 (d, J ¼ 21.0 Hz). HRMS (ESI): m/z calcd
for C18H20F2O7SNa+ (M + Na)+ 441.0790, found 441.0795.
3,4-Diuorphenyl-2,3,4,6-tetra-O-acetyl-1-thio-b-D-galacto-
pyranoside (4b)
3,4-Diuorophenyl-2,3,5-tri-O-acetyl-1-thio-b-D-xylo-furanoside (4g)
Puried by ash column chromatography Rf ¼ 0.38 (petroleum
Puried by ash column chromatography Rf ¼ 0.28 (petroleum ether/AcOEt
¼
3 : 1), white solid (29.9 mg, 74% yield);
ether/AcOEt ¼ 3 : 1), colorless oil (37.1 mg, 78% yield); [a]2D5 ¼ ꢁ56.9 (c ¼ 0.5, CHCl3); 1H NMR (400 MHz, CDCl3) d 7.35
1
[a]2D5 ¼ 6.8 (c ¼ 1.0, CHCl3); H NMR (400 MHz, CDCl3) d 7.47 (ddd, J ¼ 10.0, 7.4, 2.2 Hz, 1H), 7.24–7.19 (m, 1H), 7.11 (dt, J ¼ 10.1,
(ddd, J ¼ 10.2, 7.5, 2.2 Hz, 1H), 7.24–7.19 (m, 1H), 7.11 8.3 Hz, 1H), 5.17 (t, J ¼ 8.1 Hz, 1H), 4.94–4.85 (m, 2H), 4.73 (d, J ¼
(dt, J ¼ 10.0, 8.4 Hz, 1H), 5.41 (dd, J ¼ 3.3, 1.1 Hz, 1H), 5.18 (dd, J 8.2 Hz, 1H), 4.27 (dd, J ¼ 11.8, 4.9 Hz, 1H), 3.43 (dd, J ¼ 11.8,
¼ 9.9 Hz, 1H), 5.03 (dd, J ¼ 9.9, 3.3 Hz, 1H), 4.64 (d, J ¼ 9.9 Hz, 8.6 Hz, 1H), 2.10 (s, 3H), 2.04 (s, 6H); 13C NMR (100 MHz, CDCl3)
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d 170.0, 169.9, 169.5, 150.9 (dd, J ¼ 250.9, 12.5 Hz), 150.1 (dd, J ¼
251.7, 12.9 Hz), 130.1 (dd, J ¼ 5.9, 3.8 Hz), 128.0–127.7 (m), 122.6
(d, J ¼ 18.0 Hz), 117.8 (d, J ¼ 17.6 Hz), 85.9, 71.8, 69.7, 68.3, 65.3,
20.9, 20.9, 20.8; 19F {1H} NMR (376 MHz, CDCl3) d ꢁ135.81 (dt, J ¼
21.3, 9.2 Hz), ꢁ136.89 (m); 19F NMR (376 MHz, CDCl3) d ꢁ135.81
(d, J ¼ 21.5 Hz), ꢁ136.90 (d, J ¼ 21.4 Hz). HRMS (ESI): m/z calcd for
C17H18F2O7SNa+ (M + Na)+ 427.0634, found 427.0633.
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6-Benzo[d][1,3]dioxolyl-2,3,6,20,30,40,60-hepta-O-acetyl-1-thio-
b-cellobioside (4k)
Puried by ash column chromatography Rf ¼ 0.41 (petroleum
ether/AcOEt
¼
1 : 1), white solid (58.6 mg, 76% yield);
[a]2D5 ¼ ꢁ24.5 (c ¼ 0.5, CHCl3); 1H NMR (400 MHz, CDCl3) d 7.01
(d, J ¼ 1.8 Hz, 1H), 6.95 (dd, J ¼ 8.0, 1.8 Hz, 1H), 6.73
(d, J ¼ 8.0 Hz, 1H), 5.97 (s, 2H), 5.14 (dt, J ¼ 14.9, 9.3 Hz, 2H), 5.05
(t, J ¼ 9.6 Hz, 1H), 4.90 (dd, J ¼ 9.2, 7.9 Hz, 1H), 4.82
(t, J ¼ 9.7 Hz, 1H), 4.58 (dd, J ¼ 11.9, 2.0 Hz, 1H), 4.50 (dd, J ¼
13.5, 9.0 Hz, 2H), 4.37 (dd, J ¼ 12.5, 4.2 Hz, 1H), 4.07 (dd, J ¼ 11.9,
5.3 Hz, 1H), 4.01 (dd, J ¼ 12.5, 2.3 Hz, 1H), 3.69 (t, J ¼ 9.5 Hz, 1H),
3.65–3.56 (m, 2H), 2.12 (s, 3H), 2.08 (s, 3H), 2.06 (s, 3H), 2.01 (s,
3H), 1.99 (s, 3H), 1.99 (s, 3H), 1.97 (s, 3H); 13C NMR (100 MHz,
CDCl3) d 170.6, 170.4, 170.4, 169.9, 169.6, 169.4, 169.1, 148.6,
147.9, 128.8, 122.8, 114.8, 108.6, 101.6, 100.9, 85.8, 76.4, 73.8,
73.0, 72.1, 71.7, 70.0, 67.8, 61.9, 61.6, 20.9, 20.8, 20.7, 20.6.
Conflicts of interest
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There are no conicts to declare.
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Acknowledgements
We thank the Natural Science Foundation of China (21967011)
and the Natural Science Foundation of Jiangxi Province
(20181BBE50004), and the State Key Laboratory of Catalytic
Materials and Reaction Engineering (ZC06070008).
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