Appel-reagent-mediated transformation of glycosyl hemiacetal derivatives into thioglycosides and glycosyl thiols

Article abstract of DOI:10.3762/bjoc.9.112

A series of glycosyl hemiacetal derivatives have been transformed into thioglycosides and glycosyl thiols in a one-pot two-step reaction sequence mediated by Appel reagent (carbon tetrabromide and triphenylphosphine). 1,2-trans-Thioglycosides and β-glycosyl thiol derivatives were stereoselectively formed by the reaction of the in situ generated glycosyl bromides with thiols and sodium carbonotrithioate. The reaction conditions are reasonably simple and yields were very good.

Full text of DOI:10.3762/bjoc.9.112

Appel-reagent-mediated transformation of glycosyl
hemiacetal derivatives into thioglycosides
and glycosyl thiols
Tamashree Ghosh‡, Abhishek Santra‡ and Anup Kumar Misra*
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2013, 9, 974–982.
Bose Institute, Division of Molecular Medicine, P-1/12, C.I.T. Scheme
VII-M, Kolkata-700054, India, Fax: 91-33-2355 3886
doi:10.3762/bjoc.9.112
Received: 12 March 2013
Accepted: 29 April 2013
Published: 22 May 2013
Email:
Anup Kumar Misra* - akmisra69@gmail.com
* Corresponding author ‡ Equal contributors
Associate Editor: S. Flitsch
Keywords:
© 2013 Ghosh et al; licensee Beilstein-Institut.
License and terms: see end of document.
Appel reagent; carbon tetrabromide; glycosyl hemiacetal; glycosyl
thiol; thioglycoside; triphenylphosphine
Abstract
A series of glycosyl hemiacetal derivatives have been transformed into thioglycosides and glycosyl thiols in a one-pot two-step
reaction sequence mediated by Appel reagent (carbon tetrabromide and triphenylphosphine). 1,2-trans-Thioglycosides and
β-glycosyl thiol derivatives were stereoselectively formed by the reaction of the in situ generated glycosyl bromides with thiols and
sodium carbonotrithioate. The reaction conditions are reasonably simple and yields were very good.
Introduction
Thioglycosides (1-thiosugar) are widely used glycosyl donors in Conventionally, thioglycosides are prepared by the reaction of
glycosylation reactions [1-5]. Due to their thermal and chem- glycosyl acetates with thiols or trimethylsilylthiols in the pres-
ical stability, they have been used as stable intermediates for ence of a Lewis acid (borontrifluoride diethyletherate, stannic
functional-group transformations as well as stereoselective chloride, trimethylsilyl trifluoromethanesulfonate, etc.) [15-20].
glycosylations. Thioglycosides can be transformed into various Other methods for the synthesis of thioglycosides include (a)
other glycosyl donors [6-10] (e.g., sulfoxide, sulfone, fluoride, reduction of disulfides using metallic salts [21,22] or
bromide, hemiacetal, etc.) and hence the thio functionality is nonmetallic reducing agents (triphenylphosphine or combina-
often used as a temporary anomeric protecting group. Thiogly- tion of triethylsilane and BF3·OEt2) followed by the reaction of
cosides can act as a glycosyl donor as well as glycosyl acceptor the in situ generated thiolate ions with glycosyl bromides under
depending on the reaction conditions (orthogonal glycosyla- phase-transfer conditions [23] or in ionic liquids [24]; (b) reac-
tions) [11,12]. Due to their stability towards enzymatic hydrol- tion of glycosyl bromides with thiols under phase-transfer
ysis, several thioglycosides have been evaluated as enzyme conditions [25]; and (c) conversion of glycosyl acetates and
inhibitors [13,14]. As a consequence a large number of reports bromides to isothiouronium salts followed by hydrolytic alkyl-
have appeared in the past for the preparation of thioglycosides. ation of isothiouronium salts with alkyl halide in the presence of
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Beilstein J. Org. Chem. 2013, 9, 974–982.
a base [26,27]. Most of the reactions have several shortcomings, [45,46] which, on reaction with thiol or sodium carbonotri-
which include formation of an anomeric mixture of the prod- thioate (generated in situ from CS2 and Na2S·9H2O) [43] in
ucts, instability of the starting materials (glycosyl bromides, one-pot, could furnish thioglycosides and glycosyl thiol deriva-
etc.), multiple steps, unsatisfactory yields, use of metallic salts, tives stereoselectively. We report herein, our findings on the
use of expensive reagents, pregeneration of glycosyl isothiouro- Appel-reagent-mediated transformation of glycosyl hemiacetal
nium salts, etc. Similar to thioglycosides, glycosyl thiol deriva- derivatives to thioglycosides and glycosyl thiol derivatives
tives are useful intermediates for the synthesis of various (Scheme 1).
thiooligosaccharides, glycoproteins and glycolipids [28-32].
The anomeric configurations of glycosyl thiols mostly remain Results and Discussion
unaffected in comparison to the glycosyl hemiacetal derivatives Initially, 2,3,4,6-tetra-O-acetyl-α,β-D-glucopyranose (1;
during their synthetic transformations [4]. Glycosyl thiol deriva- 1.0 mmol) was treated with a mixture of CBr4 (1.5 mmol) and
tives act as precursors for the preparation of several glycosyl PPh3 (1.5 mmol) in CH2Cl2 (5 mL) at room temperature. The
donors such as thioglycosides [33,34], glycosyl sulfenamides starting material was consumed in 6 h to give a faster-moving
[35] and sulfonamides [36], glycosyl disulfides [37], glycosyl product (acetobromo-α-D-glucose). To the reaction mixture
thionolactones [38], etc. A number of reports are available for were added thiophenol (1.0 mmol), 10% aq Na2CO3 (5 mL) and
the preparation of glycosyl thiols, which include (a) a two-step tetrabutylammonium bromide (TBAB, catalytic) and the reac-
reaction of glycosyl halide or acetate with thiourea or thioac- tion mixture was stirred at room temperature for another 4 h.
etate and hydrolysis of the resulting intermediates [26,27]; (b) Aqueous work up of the biphasic reaction mixture furnished
reaction of hydrogen sulfide gas with glycosyl halides in phenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranoside (10)
hydrogen fluoride [39]; (c) treatment of the glycosyl hemi- in 80% yield. After a series of experimentation it was observed
acetal derivatives with Lawesson’s reagent [40] and (d) treat- that the use of 2.0 equiv each of CBr4 and PPh3 led to the full
ment of 1,6-anhydro sugar derivative [41] and glycosyl tri- consumption of compound 1 in 4 h, and addition of 1.5 equiv
chloroacetimidate derivatives [42] with bis(trimethylsilyl) thiophenol and 10% aq Na2CO3 under phase-transfer reaction
sulfide. However, most of the reactions have several inherent conditions led to the formation of compound 10 in 88% yield in
shortcomings, such as the use of reactive starting materials, an additional 4 h (Scheme 1). The reaction was carried out in a
longer reaction time, multiple steps, unsatisfactory yield, forma- set of commonly used organic solvents (e.g., toluene, EtOAc,
tion an isomeric mixture, use of expensive reagents, use of CH3OH, CH3CN, THF, DMF, DMSO, etc.) and it was observed
hazardous gases, etc. Therefore, the development of convenient that the reaction proceeds smoothly in CH2Cl2 and DMF in a
reaction conditions for the stereoselective preparation of thio- similar fashion to the first step. Since CH2Cl2 is a low-boiling-
glycosides and glycosyl thiols that are nonhazardous is perti- point solvent and can be used directly in the next step, this
nent. Recently, we reported the stereoselective preparation of solvent was chosen in the first step of the reaction (Table 1).
β-glycosyl thiol derivatives by the treatment of glycosyl bro- Increasing the quantity of the reagents (CBr4 and PPh3) did not
mide derivatives with the in situ generated sodium carbonotri- change the reaction time and yield significantly. However,
thioate (a combination of CS2 and Na2S·9H2O) [43]. Although, reducing the quantity of reagents led to a low yield of conver-
the reaction is highly stereoselective and high yielding it sion in a longer reaction time (Table 2). Under the optimized
involves the handling of unstable glycosyl bromide. Therefore, reaction conditions a series of 1,2-trans-thioglycosides were
as an extension of the earlier report [43], it was envisioned that prepared from various glycosyl hemiacetals in excellent yield
the treatment of a stable glycosyl hemiacetal derivative with (Table 3). A large-scale (5 g) preparation of compound
Appel reagent (carbon tetrabromide (CBr4) and triphenylphos- 10 was also achieved under the reaction conditions in similar
phine (PPh3)) [44] could generate the glycosyl bromide in situ, yield.
Scheme 1: Appel-reagent-mediated transformation of glycosyl hemiacetal derivatives into thioglycosides and β-glycosyl thiol derivatives in one pot.
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Beilstein J. Org. Chem. 2013, 9, 974–982.
Table 1: Screening of solvents for the in situ conversion of glycosyl
Table 2: Optimization of the in situ conversion of glycosyl hemiacetal
hemiacetal to glycosyl bromide.
to glycosyl bromide.
Entry CBr4
(equiv)
PPh3
(equiv)
Time (h) Conversion (%)
Entry
Solvent
Time (h)
Conversion (%)
1
2
3
4
5
6
7
8
CH2Cl2
CH3CN
THF
4
90
1
2
3
4
2.5
2.5
2.0
1.5
1.0
3.5
4
90
10
10
4
40a
40a
85
2.0
1.5
1.0
90
6
75a
50a
DMF
7
EtOAc
Toluene
DMSO
CH3OH
12
12
5
20a
10a
80
aThe rest of the starting material remained unreacted.
4
–b
colored solution of CS2 (2.0 mmol) and Na2S·9H2O (2.0 mmol)
(sodium carbonotrithioate) in DMF (2 mL, prepared separately)
to the reaction mixture furnished 2,3,4,6-tetra-O-acetyl-1-thio-
β-D-glucopyranose (30) in 90% yield instantly. After optimiz-
aThe rest of the starting material remained unreacted; bthe starting ma-
terial was degraded.
In another experiment, compound 1 (1.0 mmol) was treated ation of the reaction condition it was observed that the best
with a mixture of CBr4 (2.0 mmol) and PPh3 (2.0 mmol) in yield of compound 30 can be achieved by using CS2 (1.5 mmol)
CH2Cl2 (5 mL) at room temperature for 4 h. Addition of a red- and Na2S·9H2O (2.0 mmol) at room temperature. On reduction
Table 3: Appel-reagent-mediated transformation of glycosyl hemiacetal derivatives to the thioglycosides at room temperature.
Entry
1
Glycosyl hemiacetal
Thioglycoside
Time
(h)a
Yield
(%)
Ref
[49]
4
4
4
88
90
86
10
1
1
1
2
3
4
[50]
[51]
11
12
8
6
82
80
[52]
[23]
1
1
13
14
5
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Table 3: Appel-reagent-mediated transformation of glycosyl hemiacetal derivatives to the thioglycosides at room temperature. (continued)
6
7
8
4
4
90
88
[53]
[51]
2
2
15
16
8
84
–
2
17
18
9
8
6
77
80
[54]
[23]
2
2
10
19
11
8
76
–
3
20
12
4
88
[53]
3
21
13
4
8
90
88
[55]
4
4
22
23
14
–
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Beilstein J. Org. Chem. 2013, 9, 974–982.
Table 3: Appel-reagent-mediated transformation of glycosyl hemiacetal derivatives to the thioglycosides at room temperature. (continued)
15
4
6
92
85
[56]
[57]
5
6
24
25
16
17
18
19
4
4
88
85
[25]
[50]
7
7
26
27
4
4
88
85
[25]
[25]
28
29
8
9
20
aTime for the second steps after the formation of glycosyl bromides in situ.
of the quantity of CS2 and Na2S·9H2O, the rate of the reaction and glycosyl thiols were confirmed from their NMR spectral
became very slow and a considerable amount of undesired analysis (coupling constant of the H-1 (J1,2)). Appearance of the
byproducts were formed. The optimized reaction conditions coupling constant of the H-1 (J1,2) = 8–10 Hz and coupling
were applied for the preparation of a series of glycosyl thiols in constant of the SH group (JH-1,SH) = 9–10 Hz in the 1H NMR
excellent yield in a stereoselective manner (Table 4). The reac- spectra of the glycosyl thiols confirmed the exclusive forma-
tion conditions have several notable features, which include (a) tion of β-glycosyl thiols. In the case of D-mannose and L-rham-
excellent yield; (b) exceptionally high stereoselectivity; (c) one- nose, exclusive formation of β-products were unambiguously
pot two-step reaction conditions; (d) applicability for scaled-up confirmed from the coupling constant at the anomeric center
synthesis. It is worth mentioning that 1,2-trans-thioglycosides (JC-1,H-1) in the gated 1H coupled 13C NMR spectra. Coupling
and exclusively β-glycosyl thiols were formed under these constant (JC-1,H-1) = 143 Hz and 142 Hz (less than 160 Hz) in
conditions. The reaction conditions have been applied success- the gated 1H coupled 13C NMR spectra of compounds 32 and
fully for the preparation of thioglycosides and glycosyl thiols 33 confirmed the exclusive formation of β-products [47,48]. It
from D- and L-sugars as well as disaccharides. The stereo- is presumed that the reaction of the glycosyl hemiacetal deriva-
chemistry of the anomeric centers of the thioglycosides tive with the combination of CBr4 and PPh3 furnished
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Beilstein J. Org. Chem. 2013, 9, 974–982.
Table 4: Appel-reagent-mediated transformation of glycosyl hemiacetal derivatives to glycosyl thiol derivatives at room temperature.
Entry
1
Glycosyl hemiacetal
Glycosyl thiol
Timea (min)
Yield (%)
90
Ref
[41]
5
1
2
30
2
3
5
5
92
85
[58]
[59]
31
32
3
4
5
4
5
6
5
5
90
88
[60]
[41]
33
34
15
15
86
85
[61]
[62]
7
35
36
7
8
aTime for the second steps after formation of glycosyl bromides in situ.
α-glycosyl bromide in the first step. Interconversion of the homogeneous solution led to the exclusive formation of the
α-glycosyl bromide to the reactive β-glycosyl bromide in the β-glycosyl thiol derivative (Scheme 2).
presence of a catalytic bromide ion derived from TBAB, led to
the formation of a 1,2-oxocarbonium ion by participation of the Conclusion
neighboring group, which finally furnished 1,2-trans-thioglyco- In summary, treatment of glycosyl hemiacetal derivatives with
side by the reaction of thiols under reasonably slow biphasic Appel reagent followed by reaction with thiols and sodium
reaction conditions. The thioglycoside formation became very carbonotrithioate (derived from the reaction of CS2 and
slow without the addition of TBAB and the same product was Na2S·9H2O) furnished thioglycosides and glycosyl thiols in
obtained in a poor yield over a much longer period of time. In excellent yield with high stereoselectivity in a two-step, one-pot
contrast, rapid SN2-substitution of the bromide ion at the reaction condition. The reaction condition is operationally
anomeric center in α-glycosyl bromide with a carbonotrithioate simple, mild, reproducible, high-yielding, highly stereoselec-
ion (derived from the reaction of CS2 and Na2S·9H2O) in tive, and can be scaled up for large-scale preparation. These
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Beilstein J. Org. Chem. 2013, 9, 974–982.
Scheme 2: Plausible mechanistic pathways for the formation of 1,2-trans-thioglycoside and β-glycosyl thiol.
reaction conditions may be considered as a valuable addition to 10.0 Hz each, 1H, H-2), 5.17 (dd, J = 10.0, 3.5 Hz, 1H, H-3),
those existing in this area.
4.12–4.10 (m, 2H, H-5, H-6a), 4.08–4.06 (m, 1H, H-6b), 2.15,
2.05, 2.01, 1.99 (4 s, 12H, 4 COCH3); 13C NMR (125 MHz,
CDCl3) δ 170.1, 169.9, 169.6, 169.5 (4 COCH3), 133.3–124.1
Experimental
General methods: All reactions were monitored by thin-layer (Ar-C), 84.2 (C-1), 75.2 (C-3), 71.6 (C-4), 67.1 (C-5), 67.0
chromatography over silica-gel-coated TLC plates. The spots on (C-2), 60.9 (C-6), 20.7, 20.6, 20.5, 20.4 (4 COCH3); ESIMS
TLC were visualized by warming ceric sulfate (2% Ce(SO4)2 in (m/z): 531.1 [M + Na]+; Anal. calcd for C21H24N4O9S
2 N H2SO4) sprayed plates on a hot plate. Silica gel 230–400 (508.12): C, 49.60; H, 4.76; found: C, 49.45; H, 4.94.
mesh was used for column chromatography. 1H and 13C NMR
spectra were recorded on Bruker Avance 500 MHz by using 1-Phenyl-1H-tetrazol-5-yl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-
CDCl3 as solvent and TMS as internal standard, unless stated mannopyranoside (20): Yellow oil; [α]D25 −2 (c 1.2, CHCl3);
otherwise. Chemical shift values are expressed as δ in parts per IR (neat): 3104, 2838, 1610, 1520, 1472, 916, 697 cm−1; 1H
million. ESIMS were recorded on a Micromass mass spectrom- NMR (500 MHz, CDCl3) δ 7.61–7.50 (m, 5H, Ar-H), 6.12 (br
eter. Commercially available grades of organic solvents of s, 1H, H-1), 5.68 (d, J = 2.5 Hz, 1H, H-2), 5.27 (t, J = 10.0 Hz
adequate purity were used in all reactions.
each, 1H, H-4), 5.19 (dd, J = 10.0, 3.0 Hz, 1H, H-3), 4.31 (dd, J
= 12.5, 5.5 Hz, 1H, H-6a), 4.13 (d, J = 12.5 Hz, 1H, H-6b),
3.91–3.88 (m, 1H, H-5), 2.19, 2.07, 2.05, 1.99 (4 s, 12H, 4
COCH3); 13C NMR (125 MHz, CDCl3) δ 170.1, 170.0, 169.7,
General experimental conditions for the
preparation of thioglycosides
To a solution of glycosyl hemiacetal (1.0 mmol) in dry CH2Cl2 169.6 (4 COCH3), 130.5–124.1 (Ar-C), 82.6 (C-1), 77.2 (C-3),
(5 mL) were added CBr4 (2.0 mmol) and PPh3 (2.0 mmol) and 71.5 (C-4), 70.1 (C-5), 65.0 (C-2), 62.0 (C-6), 20.7, 20.6, 20.5,
the reaction mixture was stirred at room temperature for 4 h. 20.4 (4 COCH3); ESIMS (m/z): 531.1 [M + Na]+; Anal. calcd
After consumption of the starting material (TLC, for C21H24N4O9S (508.12): C, 49.60; H, 4.76; found: C, 49.42;
hexane–EtOAc 2:1), thiophenol (1.5 mmol), 10% aq. Na2CO3 H, 4.97.
(5 mL) and TBAB (20 mg) were added to the reaction mixture,
and it was stirred for the appropriate time mentioned in Table 3. 1-Phenyl-1H-tetrazol-5-yl 2,3,4-tri-O-acetyl-1-thio-α-L-
The reaction mixture was diluted with water and extracted with rhamnopyranoside (23): Yellow oil; [α]D25 +19 (c 1.2,
CH2Cl2 (50mL). The organic layer was washed with water, CHCl3); IR (neat): 3106, 2836, 1600, 1502, 1457, 916, 699
dried (Na2SO4) and concentrated to give the crude product, cm−1; 1H NMR (500 MHz, CDCl3) δ 7.59–7.50 (m, 5H, Ar-H),
which was purified over SiO2 by using hexane–EtOAc as eluant 6.10 (d, J = 1.0 Hz, 1H, H-1), 5.66 (d, J = 3.5, 1.0 Hz, 1H, H-2),
to give the pure product. Known compounds gave spectral data 5.13 (dd, J = 10.0, 3.0 Hz, 1H, H-3), 5.06 (t, J = 9.5 Hz each,
identical to the data reported in the cited references.
1H, H-4), 3.80–3.75 (m, 1H, H-5), 2.18, 2.07, 1.97 (3 s, 9H, 3
COCH3), 1.28 (d, J = 6.0 Hz, 3H, CH3); 13C NMR (125 MHz,
1-Phenyl-1H-tetrazol-5-yl 2,3,4,6-tetra-O-acetyl-1-thio-β-D- CDCl3) δ 170.1, 170.0, 169.9 (3 COCH3), 130.4–124.1 (Ar-C),
galactopyranoside (17): Yellow oil; [α]D25 +15 (c 1.2, CHCl3); 82.4 (C-1), 75.6 (C-5), 71.4 (C-3), 70.5 (C-4), 69.8 (C-2), 20.7,
IR (neat): 3114, 2842, 1612, 1522, 1467, 912, 699 cm−1; 1H 20.6, 20.5 (3 COCH3), 17.6 (CH3); ESIMS (m/z): 473.1 [M +
NMR (500 MHz, CDCl3) δ 7.58–7.52 (m, 5H, Ar-H), 5.80 (d, J Na]+; Anal. calcd for C19H22N4O7S (450.12): C, 50.66; H,
= 10.0 Hz, 1H, H-1), 5.46 (d, J = 3.0 Hz, 1H, H-4), 5.34 (t, J = 4.92; found: C, 50.47; H, 5.15.
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Beilstein J. Org. Chem. 2013, 9, 974–982.
General experimental condition for the
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