A strategy for the synthesis of anthraquinone-based aryl- C -glycosides

Article abstract of DOI:10.1021/jo302589t

An efficient and simple strategy for the synthesis of a diverse range of anthraquinone-based aryl-C-glycosides has been developed. It involves the sequential Diels-Alder reaction and oxidative aromatization with the preformed glycosyl diene and dienophiles. The glycosyl dienes were obtained from simple sugars by tandem one-pot substitution and elimination reaction.

Full text of DOI:10.1021/jo302589t

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Article
A Strategy for the Synthesis of Anthraquinone based Aryl-C-Glycosides
Namrata Anand, Kapil Upadhyaya, Arya Ajay, Rohit Mahar,
Sanjeev K. Shukla, Brijesh Kumar, and Rama Pati Tripathi
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo302589t • Publication Date (Web): 25 Apr 2013
Downloaded from http://pubs.acs.org on April 28, 2013
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A Strategy for the Synthesis of Anthraquinone based Aryl-C-Glycosides
Namrata Anand†, Kapil Upadhyaya†, Arya Ajay†, Rohit Mahar‡, Sanjeev K. Shukla‡, Brijesh
Kumar‡, and Rama Pati Tripathi*†
†Division of Medicinal and Process Chemistry, CSIR-Central Drug Research Institute, Lucknow
226001, India
‡Sophisticated Analytical Instrument Facility, CSIR-Central Drug Research Institute, Lucknow
226001, India
rpt.cdri @gmail.com
ABSTRACT:
An efficient and simple strategy for the synthesis of diverse range of anthraquinone based aryl-
C-glycosides has been developed. It involves the sequential Diels-Alder reaction and oxidative
aromatization with the preformed glycosyl diene and dienophiles. The glycosyl dienes were
obtained from simple sugars by tandem one pot substitution and elimination reaction.
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INTRODUCTION:
Secondary metabolites, frequently available as glycosides, produced by plants and
microorganisms have been the most important chemical entities till date as bioactives. The aryl-
C-glycosides, both of synthetic and natural origins, are of great significance1 in medicinal
chemistry owing to their stability towards the enzymatic and chemical hydrolysis as compared to
the O-glycosides.2 They are well known antibiotics, potent enzyme inhibitors and possess a wide
range of biological activities.3 Currently several aryl-C-glycosides as SGLT2 inhibitors are
undergoing clinical trials for the treatment of diabetes and related complications.4 The
angucycline group of glycosides with anthraquinone as aglycon part are endowed with
anticancer, antibacterial, antiviral, enzyme inhibitory, and platelet aggregation inhibition
activities.3
Synthesis of anthraquinone based aryl-C-glycosides has been the focus of several leading
research groups for quite some time.5 In view of the structural complexity of aglycones, the
control of regiochemistry in glycosylation of a polysubstituted aromatic precursor to get the
desired aryl-C-glycosides is a crucial issue. To overcome this, the benzannulation or
cycloaddition strategies for glycosylated aromatics have played key roles.6 Suzuki’s group has
developed elegant methods for the total synthesis of gilvocarcin and ravidomycin using
cycloaddition reaction of sugar bearing benzyne and substituted furans7. Later on furan-benzyne
cycloaddition to get aryl-C-glycosides was extended by Martin’s group with benzyne precursors
as quinone equivalents to get the aryl-C-glycosides.8 A sequential intermolecular enyne
metathesis of C-alkynyl glycosides with ethylene and subsequent Diels-Alder reaction followed
by aromatization reaction9, and Diels-Alder reactions of preformed C-pentadienyl glycosides
with quinones10 were also used for the synthesis of aryl-C-glycosides. Thus, the direct Diels-
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Alder reaction of dienyl glycosides with quinones has rarely been used to get aryl-C-glycosides
possibly due to (i) difficulties to access dienyl glycosides, (ii) the drastic conditions required for
the cycloaddition between dienyl glycosides and quinones, (iii) cost of Grubbs’ second
generation catalyst used in metathesis reactions, and (iv) difficulty in deprotection of the
protecting groups to get the glycosides with free hydroxyl groups. Therefore, an economical,
environmently benign and high yield synthesis of aryl-C-glycosides is still a priority area of
research. In continuation of our ongoing research on aryl-C-glycosides11 and glycoconjugates12
as chemotherapeutics, we reported herein a robust, eco-friendly, and economical viable
stereoselective synthesis of anthraquinone C-glycosides involving a simple synthesis of glycosyl
dienes via Et3N catalyzed sequential O-methanesulfonylation and elimination reactions of
glycosyl butenols followed by sequential Diels-Alder reaction of these dienes with dienophiles
and oxidative aromatization.
RESULTS AND DISCUSSION:
The required butadienyl glycoside (3a-3o) substrates for Diels-Alder reaction were prepared
(Scheme 1) in good yields (82-93 %) with EE-stereoselectivity from preformed butenoyl
glycosides (1a-1o)13.
Scheme 1. Synthesis of glycosylated dienes
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*(purely isolated (EE) diene was used for deacetylation and this deacetylated diene was directly used in
cycloaddition reaction)
Luche reduction14 of butenoyl-C-glycosides (1a-1o) with NaBH4/CeCl3.6H2O in methanol
yielded the glycosides (2a-2o) as (1:1) diastereoisomeric mixtures in excellent yields (89-97 %).
The latter on Et3N catalysed tandem one pot in situ methanesulfonylation and elimination
reaction provided respective dienyl glycosides (3a-3o) (Scheme 1). Optimization of this step
was made using two different sulfonylating agents tosyl chloride (TsCl) or mesyl chloride
(MsCl) and organic bases (DBU, DABCO or Et3N) with a model glycosyl butenol substrate 2a,
where MsCl (2 eq.)-Et3N (1.2 eq.) combination proved to be the optimum for the synthesis of
dienyl glycoside 3a (entry 5, Table 1).
Table 1 Optimization of reaction conditions for glycosyl diene
entry alkylating
agent
base
time tempb Yield
(h)
(°C)
(%)
TsCl
TEA
4
40
nrc
1
TsCl
TsCl
TsCl
MsCl
MsCl
MsCl
MsCl
DBU
10
10
10
4
40
70
70
40
40
40
70
nr
2
3
4
5
6
7
8
TEA
nr
DABCO
TEA
nr
90d
50
nr
DBU
4
DABCO
DABCO
10
8
20
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a = all reactions were carried out in CH2Cl2( 0.4 M), b = high temperature reactions were performed in sealed tube, c
= no reaction, d = isolated yield.
Following the optimized reaction conditions, 3a-3o were obtained as a mixture of EE (major,
85-90 %) and ZE (minor, 10-15 %) isomers in excellent yields (Table 2). The structures of the
two isomers were well established by detailed NMR studies (See Supporting Information).
Table 2. Synthesized glycosylated dienesa (3b-3o, 4a and 4b)
entry product
Ar
R1
H
R2
R3
CH2OAc
CH2OAc
CH2OAc
CH2OAc
CH2OAc
CH2OAc
CH2OAc
H
yieldb (%)
91
1
2
phenyl
OAc
OAc
OAc
OAc
OAc
OAc
OAc
OAc
OAc
OAc
OAc
OAc
H
3b
3c
3d
3e
3f
4-Br-phenyl
4-Cl-phenyl
2-Cl-phenyl
4-iPr-phenyl
4-OMe-phenyl
2-naphthyl
phenyl
H
89
3
H
84
4
H
87
5
H
92
6
H
92
3g
3h
3i
7
H
82
8
H
90
9
4-Cl-phenyl
4-F-phenyl
4-Me-phenyl
4-OMe-phenyl
4-Me-phenyl
4-OMe-phenyl
4-F-phenyl
H
H
86
3j
10
11
12
13
14
15
H
H
85
3k
3l
H
H
92
H
H
91
3m
3n
3o
4a
OAc
OAc
H
CH2OAc
CH2OAc
H
92
H
93
OH
97c
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4-OMe-phenyl
H
OH
H
96c
4b
a = The dienes were synthesized from respective glycosyl butenols using MsCl (2 eq)-Et3N (1.2 eq) in CH2Cl2 at
40° C, b = yields were calculated for the mixture of isomers, c = yields for purely isolated acetylated (EE) dienes
Zemplen deacetylation of dienyl glycosides 3k (EE) and 3m (EE) resulted in predominantly (EE)
isomer of deacetylated glycosyl dienes 4a and 4b respectively in good yields (Scheme 1, Table
2).
The optimization of cycloaddition reaction of (EE) dienyl-1-β-D-xylopyranoside 3l was carried
out with naphthoquinone under different conditions (Table 3). The reaction was unsuccessful up
to 40 °C in presence or absence of any catalyst. Heating the reaction mixture in presence of
different Lewis acid catalysts at 80 °C in different solvents led to the formation of desired C-
(1,4-dihydroanthraquinon-1-yl-)-xylopyranoside (5'l) in varying yields.
Table 3. Optimization of reaction conditions for Diels-Alder reaction
catalyst
(mol %)
Time
(h)
temperature
(°C)
yield
(%)
nrb
entry
solventa
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
1
2
3
4
5
6
7
8
No catalyst
10
110
AlCl3 (5)
ZnCl2 (5)
5
5
6
6
6
3
3
100
80
nr
40
50
nr
SnCl2 (5)
80
CuCl2 (5)
100
100
80
CoCl2 (5)
nr
FeCl3.6H2O (5)
InCl3.4H2O (5)
95
99
80
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9
Anhyd. InCl3 (5)
InCl3.4H2O (5)
InCl3.4H2O (5)
InCl3.4H2O (5)
InCl3.4H2O (5)
InCl3.4H2O (5)
InCl3.4H2O (2)
InCl3.4H2O (10)
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dry toluene
ethanol
DMF
80
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80
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96
nr
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30
85
30
nr
acetonitrile
dioxane
water
toluene
toluene
67
63c
a = 0.25 M solvents used, b = no reaction, c = complex mixture therefore low yield.
Among the different catalysts screened, AlCl3, CuCl2, and CoCl2 were found to be ineffective,
while ZnCl2 and SnCl2 were moderetly effective with 40-50 % yields of desired product.
However, FeCl3.6H2O and InCl3.4H2O were the most effective to give the maximum yields of 5'l
(entries 7 and 8, Table 3). The reaction proceeded equally well with anhydrous InCl3 in dry
toluene, indicating no significant role of water during reaction (entry 9, Table 3). The effect of
solvents were also examined (Table 3), while the polar protic solvents were almost ineffective
(entries 10 and 14, Table 3) the aprotic polar solvents were somewhat effective (entries 11-13,
Table 3) and aprotic nonpolar solvent (toluene) was found to be the most effective (entries 7 and
8, Table 3) with >95 % conversion of 3l into product 5'l, (Scheme 2). Therefore, for Diels-Alder
reaction 0.25 M toluene as solvent, InCl3.4H2O as catalyst at 80 °C heating was chosen as the
optimum reaction condition for subsequent reactions. Compound 5'l was isolated, characterized,
and was found to be an inseparable diastereoisomeric mixture (NMR). Finally, oxidation of 5'l
with molecular O2/Et3N allows us to get the aryl-C- xylopyranoside 5l in 98 % yield.
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Scheme 2: Synthesis of aryl-C-glycoside
The above two steps transformation of dienyl glycoside 3l to aryl C-glycoside 5l was also carried
out without the purification of the intermediate dihydro product 5’l in 95 % yield (Scheme 2).
Since the diastereomeric centres were lost during oxidative aromatization, the presence of the
isomeric mixture of dienes did not affect the sequential reactions and therefore these mixtures
were used as such for subsequent cycloaddition and oxidative aromatization reactions (Table 4).
Based on the above observations, we have extended the scope of this cycloadditive oxidation
reaction to other dienyl glycosides derived from D-glucose, D-xylose and D-mannose with
naphthoquinone as a dienophiles to get structurally diverse aryl-C-β-D-glycosides (Table 4).
Table 4 Synthesized aryl-C-β-D-glycosidesa
entry
1
dienes aryl-C-glycosides
yieldb
(%)
92
3a
2
91
3b
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4a
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a = for reaction molarity see the experimental section, b = isolated yield
We were also successful in synthesizing unprotected aryl-C-glycosides 6a and 6b by reacting the
polar unprotected dienyl glycosides 4a and 4b respectively with naphthoquinone in water:
toluene (9:1) at 80 °C followed by oxidative aromatization in very good yields (entries 16 and
17, Table 4).
The scope of the Diels-Alder reaction of dienyl glycosides was extended by reacting dienyl
glycoside 3m with N-phenyl maleimide as dienophile to give the cycloaddition endo product 4-
(2',3',4',6'-tetra-O-acetyl-β-D-xylopyranosyl)-7-(4-methoxyphenyl)-2-phenyl
tetrahydro-1H-
isoindole-1,3(2H)-dione (7) exclusively in good yield (81 %) (Scheme 3). The structure of the
latter was established on the basis of detailed NMR experiments (SI). However, the product 7
could not be aromatized under the oxidative aromatization reaction conditions.
Scheme 3: Synthesis of maleimide adduct 7
CONCLUSIONS:
We have reported a simple but efficient strategy to get aryl-C-β-D-glycosides with increasing
opportunities for diversity generation. This strategy holds potential to access a library of
anthraquinone based C-glycosides and related analogues of great medicinal values. The method
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involved is economical and eco-friendly with no sophistication. The extended scope of this
strategy may lead to cycloaddition products with different functional groups on the glycosides.
EXPERIMENTAL SECTION
General Chemistry:
Commercially available reagent grade chemicals were used as received. Reactions were
monitored by TLC, with detection by UV light, spraying a 5 % H2SO4 ethanolic solution and
applying heat. Column chromatography was performed on silica gel (60-120 mesh). IR spectra
1
were recorded as thin films or in KBr solution. H and 13C NMR spectra were recorded on
Bruker 200, 300 and 400 MHz spectrometer in CDCl3 or DMSOd6. Chemical shift values were
reported in ppm relative to TMS (tetramethylsilane) as internal reference, unless otherwise
stated; s (singlet), d (doublet), t (triplet), dd (doublet of doublet), m (multiplet); J in hertz. The
chemical shift assignments of prototypes were carried out with the help of 2D NMR experiments
as COSY, HSQC, HMBC and NOESY. HRMS spectra were performed using a mass
spectrometer Q-TOF. Optical rotation was recorded on Autopol III, S. No. 301, manufactured by
Rudolph Research Analytical, USA.
General procedure for the synthesis of 1-glycosyl-4-phenyl butene-2-ols (2a-2o)
(E)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-2(R/S)-hydroxy-4-(4-
fluorophenyl)but-3-ene (2a): To a magnetically stirred solution of E-butenoyl-C-glycoside 1a
(2.00 g, 4.04 mmol) in methanol (5 mL, 0.81 M) at 0 °C, CeCl3.6H2O (1.32 g, 4.04 mmol) and
NaBH4 (0.15 g, 4.04 mmol) were sequentially added. The solution was allowed to stir for 0.5 h at
0 °C, till the completion of reaction (TLC). Excess of NaBH4 was quenched by saturated
aqueous solution of NH4Cl (10 mL), reaction mixture was filtered and washed with methanol.
The filtrate was evaporated under reduced pressure to get a crude mass which was extracted with
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ethyl acetate and water. Ethyl acetate layer was dried (anhyd. Na2SO4) and concentrated under
reduced pressure to afford a crude residue, which was purified by column chromatography (SiO2,
60-120 mesh) using a gradient of hexane: ethyl acetate (15:7) as eluent to give (1:1)
diastereoisomeric mixture of the above compound 2a in 95 % yield (1.88 g) as white solid: mp
135-137 °C; IR (KBr) νmax cm-1: 3420, 3302, 1749, 1640, 776; [α]25D –28.16° (c 0.1, CHCl3); 1H
NMR (300 MHz, CDCl3 + CCl4) δ 7.37-7.31 (m, 2H, ArH), 7.04-6.98 (m, 2H, ArH), 6.63 (d, J3,4
= 15.9 Hz, 1H, H-4), 6.16-6.05 (m, 1H, H-3), 5.21-5.15 (m, 1H, H-3´), 5.11-5.03 (m, 1H, H-2´),
5.00-4.92 (m, 1H, H-4´), 4.56-4.52 (m, 1H, H-2), 4.26-4.13 (m, 2H, H-6´a, H-6´b), 3.74-3.66 (m,
2H, H-1´, H-5´), 3.09 (s, 1H, OH), 2.11 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.04 (s, 3H, OAc), 2.01
13
(s, 3H, OAc), 1.82-1.76 (m, 2H, CH2); C NMR (75 MHz, CDCl3) δ 170.8, 170.2, 169.4 (2C),
164.0 (d, 1JCF = 248.8 Hz), 132.8, 130.7, 129.5, 128.8 (2C, d, 3JCF = 8.0 Hz), 115.7 (2C, d, 2JCF
=
21.6 Hz), 75.9, 74.9, 74.0, 71.9, 71.4, 68.6, 62.5, 38.6, 20.7 (4C); ESI-HRMS calcd for
C24H29FO10Na ([M+Na]+) 519.1637 found 519.1637.
(E)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-2(R/S)-hydroxy-4-phenyl
but-3-ene
(2b): It was obtained by the reaction of E-butenoyl-C-glycoside 1b (2.0 g, 4.20 mmol) in
methanol (5 mL, 0.84 M) with CeCl3.6H2O (1.37 g, 4.20 mmol) and NaBH4 (0.16 g, 4.20 mmol)
at 0 °C in 94 % yield (1.88 g) as white solid: mp 108-110 °C; IR (KBr) νmax cm-1: 3356, 1748,
1640, 1219, 771; [α]25D –80.53° (c 0.1, CHCl3); 1H NMR (300 MHz, CDCl3 + CCl4) δ 7.37-7.21
(m, 5H, ArH), 6.65-6.57 (m, 1H, H-4), 6.24-6.12 (m, 1H, H-3), 5.20-5.08 (m, 1H, H-3´), 5.04 (t,
J = 9.8 Hz, 1H, H-2´), 4.96 (t, J = 9.5 Hz, 1H, H-4´), 4.55-4.53 (m, 1H, H-2), 4.24- 4.10 (m, 2H,
H-6´a, H-6´b), 3.68-3.65 (m, 2H, H-1´, H-5´), 2.90 (s, 1H, OH), 2.10 (s, 3H, OAc), 2.05 (s, 3H,
OAc), 2.03 (s, 3H, OAc), 2.00 (s, 3H, OAc), 1.88-1.76 (m, 2H, CH2); 13C NMR (50 MHz, CDCl3
+ CCl4) δ 170.3, 170.0, 169.2, 169.1, 136.5, 131.0, 130.5, 128.5, 127.7 (2C), 126.4, 126.4, 76.3,
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75.9, 73.9, 71.8, 71.2, 68.5, 62.3, 38.4, 20.7 (2C), 20.5 (2C); ESI-HRMS calcd for C24H30O10Na
([M+Na]+) 501.1731 found 501.1730.
(E)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-2(R/S)-hydroxy-4-(4-
bromophenyl)but-3-ene (2c): It was obtained by the reaction of E-butenoyl-C-glycoside 1c (2.0
g, 3.61 mmol) in methanol (5 mL, 0.72 M) with CeCl3.6H2O (1.18 g, 3.61 mmol) and NaBH4
(0.135 g, 3.61 mmol) at 0 °C in 96 % yield (1.92 g) as white solid: mp 155-157 °C; IR (KBr)
1
νmax cm-1: 3412, 1748, 1640, 1278, 776; [α]25 –69.13° (c 0.1, CHCl3); H NMR (300 MHz,
D
CDCl3) δ 7.46 (d, J = 8.2 Hz, 2H, ArH), 7.26 (d, J = 8.3 Hz, 2H, ArH), 6.60 (d, J = 15.8 Hz, 1H,
H-4), 6.18 (dd, J2,3 = 3.3 Hz, J3,4 = 15.8 Hz, 1H, H-3), 5.19 (t, J = 9.3 Hz, 1H, H-3´), 5.04 (t, J =
9.7 Hz, 1H, H-2´), 4.94 (t, J = 9.5 Hz, 1H, H-4´), 4.54-4.52 (m, 1H, H-2), 4.26 (dd, J 6´a,6´b = 12.2
Hz, J5´,6´b = 2.0 Hz, 1H, H-6´a), 4.16-4.10 (m, 1H, H-6´b), 3.72-3.69 (m, 2H, H-1´, H-5´), 3.01 (s,
1H, OH), 2.11 (s, 3H, OAc), 2.06 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.01 (s, 3H, OAc), 1.85-1.80
(m, 2H, CH2); 13C NMR (50 MHz, CDCl3) δ 170.6, 170.3, 169.4 (2C), 135.5, 131.7 (2C), 129.2
(2C), 128.0 (2C), 121.5, 75.9(2C), 73.9, 71.8, 71.4, 68.6, 62.4, 38.4, 20.7 (2C), 20.6 (2C); ESI-
HRMS calcd for C24H29BrO10Na ([M+Na]+) 579.0836 found 579.0835.
(E)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-2(R/S)-hydroxy-4-(4-
chlorophenyl)but-3-ene (2d): It was obtained by the reaction of E-butenoyl-C-glycoside 1d (2.0
g, 3.92 mmol) in methanol (5 mL, 0.78 M) with CeCl3.6H2O (1.28 g, 3.92 mmol) and NaBH4
(0.14 g, 3.92 mmol) at 0 °C in 93% yield (1.86 g) as white solid: mp 145-147 °C; IR (KBr) νmax
cm-1: 3421, 1748, 1637, 1234, 778; [α]25D –65.13° (c 0.1, CHCl3); 1H NMR (400 MHz, CDCl3 +
CCl4) δ 7.28 (bs, 4H, ArH), 6.61 (d, J = 15.8 Hz, 1H, H-4), 6.21-6.12 (m, 1H, H-3), 5.22-5.15
(m, 1H, H-3´), 5.09-5.00 (m, 1H, H-2´), 4.97-4.91 (m, 1H, H-4´), 4.58-4.52 (m, 1H, H-2), 4.11
(dd, J 6´a,6´b = 12.2 Hz, J5´,6´a = 2.0 Hz, 1H, H-6´a) 4.24 (m, 1H, H-6´b), 3.73-3.65 (m, 2H, H-1´,
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H-5´), 3.00 (s, 1H, OH), 2.09 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.03 (s, 3H, OAc), 2.02 (s, 3H,
OAc), 1.83-1.77 (m, 2H, CH2); 13C NMR (100 MHz, CDCl3) δ 170.9, 170.5, 169.8, 169.6, 135.3,
133.5, 132.5, 131.9, 129.4, 128.9, 127.9, 127.8, 76.14, 75.2, 74.1, 72.1, 71.5, 68.8, 62.6, 38.6,
20.9, 20.8, 20.8, 20.7; ESI-HRMS calcd for C24H29ClO10Na ([M+Na]+) 535.1341 found
535.1341.
(E)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-2(R/S)-hydroxy-4-(2-
chlorophenyl)but-3-ene (2e): It was obtained by the reaction of E-butenoyl-C-glycosides 1e
(2.0 g, 3.92 mmol) in methanol (5 mL, 0.78 M) with CeCl3.6H2O (1.28 g, 3.92 mmol) and
NaBH4 (0.14 g, 3.92 mmol) at 0 °C in 91 % yield (1.82 g) as white solid: mp 152-155 °C; IR
1
(KBr) νmax cm-1: 3425, 1752, 1648, 1234, 776; [α]25 –57.99° (c 0.1, CHCl3); H NMR (300
D
MHz, CDCl3) δ 7.51 (d, J = 8.2 Hz, 2H, ArH), 7.33-7.31 (m, 2H, ArH), 6.65 (d, J = 15.6 Hz, 1H,
H-4), 6.30-6.19 (m, 1H, H-3), 5.29-5.21 (m, 1H, H-3´), 5.12-4.96 (m, 2H, H-2´, H-4´), 4.61-4.57
(m, 1H, H-2), 4.31-4.09 (m, 2H, H-6´a, H-6´b), 3.79-3.72 (m, 2H, H-1´, H-5´), 3.08 (s, 1H, OH),
2.16 (s, 3H, OAc), 2.11 (s, 3H, OAc), 2.10 (s, 3H, OAc), 2.05 (s, 3H, OAc), 1.90-1.85 (m, 2H,
CH2); 13C NMR (75 MHz, CDCl3) δ 170.7, 170.3, 169.6, 169.5, 135.6, 131.8 (2C), 131.7, 129.3,
128.0 (2C), 121.6, 75.9, 73.9, 71.9, 71.4, 68.6 (2C), 62.4, 38.4, 20.7 (2C), 20.6 (2C); ESI-HRMS
calcd for C24H29ClO10Na ([M+Na]+) 535.1341 found 535.1342.
(E)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-2(R/S)-hydroxy-4-(4-
isopropylphenyl)but-3-ene (2f): It was obtained by the reaction of E-butenoyl-C-glycoside 1f
(2.0 g, 3.84 mmol) in methanol (5 mL, 0.77 M) with CeCl3.6H2O (1.26 g, 3.84 mmol) and
NaBH4 (0.14 g, 3.84 mmol) at 0 °C in 94 % yield (1.88 g) as white solid: mp 103-105 °C; IR
1
(KBr) νmax cm-1: 3331, 1746, 1613, 1228, 689; [α]25 –85.70° (c 0.1, CHCl3); H NMR (300
D
MHz, CDCl3 + CCl4) δ 7.30 (d, J = 2.5 Hz, 2H, ArH), 7.17 (d, J = 7.0 Hz, 2H, ArH), 6.68-6.54
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(m, 1H, H-4), 6.19-6.07 (m, 1H, H-3), 5.13 (t, J = 9.4 Hz, 1H, H-3´), 5.04 (t, J = 9.8 Hz, 1H, H-
2´), 4.94 (t, J = 9.5 Hz, 1H, H-4´), 4.54-4.50 (m, 1H, H-2), 4.22-4.10 (m, 2H, H-6´a, H-6´b),
3.68-3.60 (m, 2H, H-1´, H-5´), 2.94-2.85 (m, 1H, CH), 2.82 (s, 1H, OH), 2.11 (s, 3H, OAc), 2.04
(s, 3H, OAc), 2.03 (s, 3H, OAc), 2.00 (s, 3H, OAc), 1.79-1.74 (m, 2H, CH2), 1.26 (s, 3H, CH3),
1.24 (s, 3H, CH3); 13C NMR (50 MHz, CDCl3 + CCl4) δ 170.3, 170.0, 169.2 (2C), 148.5, 134.1,
130.5, 130.0, 126.6 (2C), 126.4 (2C), 75.9, 74.9, 74.0, 71.8, 71.3, 68.5, 62.3, 38.4, 33.8, 23.9
(2C), 20.5 (4C); ESI-HRMS calcd for C27H36O10Na ([M+Na]+) 543.2201 found 543.2201.
(E)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-2(R/S)-hydroxy-4-(4-
methoxyphenyl)but-3-ene (2g): It was obtained by the reaction of E-butenoyl-C-glycoside 1g
(2.0 g, 3.93 mmol) in methanol (5 mL, 0.79 M) with CeCl3.6H2O (1.28 g, 3.93 mmol) and
NaBH4 (0.15 g, 3.93 mmol) at 0 °C in 94 % yield (1.88 g) as white solid: mp 95-97 °C; IR (KBr)
1
νmax cm-1: 3556, 1745, 1640, 1278, 791; [α]25 –89.70° (c 0.1, CHCl3); H NMR (300 MHz,
D
CDCl3 + CCl4) δ 7.29-7.26 (m, 2H, ArH), 6.84 (d, J = 8.6 Hz, 2H, ArH), 6.57 (d, J = 15.5 Hz,
1H, H-4), 6.08-5.97 (m, 1H, H-3), 5.10 (t, J = 9.4 Hz, 1H, H-3´), 5.07-4.97 (m, 1H, H-2´), 4.91
(t, J = 9.6 Hz, 1H, H-4´), 4.51-4.46 (m, 1H, H-2), 4.23-4.09 (m, 2H, H-6´a, H-6´b), 3.80 (s, 3H,
OCH3), 3.66-3.60 (m, 2H, H-1´, H-5´), 2.80 (s, 1H, OH), 2.09 (s, 3H, OAc), 2.04 (s, 3H, OAc),
13
2.02 (s, 3H, OAc), 1.99 (s, 3H, OAc), 1.87-1.73 (m, 2H, CH2); C NMR (50 MHz, CDCl3 +
CCl4) δ 170.3, 170.0, 169.1 (2C), 159.3, 131.9, 130.2, 129.2, 128.7, 127.6, 113.4 (2C), 75.8,
74.0, 71.8, 71.4, 68.5 (2C), 62.3, 55.1, 38.4, 20.5 (4C); ESI-HRMS calcd for C25H32O11Na
([M+Na]+) 531.1837 found 531.1836.
(E)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-2(R/S)-hydroxy-4-(2-
naphathalenyl)but-3-ene (2h): It was obtained by the reaction of E-butenoyl-C-glycoside 1h
(2.0 g, 3.80 mmol) in methanol (5 mL, 0.76 M) with CeCl3.6H2O (1.24 g, 3.80 mmol) and
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NaBH4 (0.14 g, 3.80 mmol) at 0 °C in 89 % yield (1.78 g) as white solid: mp 112-115 °C; IR
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(KBr) νmax cm-1: 3436, 1749, 1640, 1237, 774; [α]25 –54.64° (c 0.1, CHCl3); H NMR (300
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MHz, CDCl3 + CCl4) δ 7.87-7.78 (m, 1H, ArH), 7.61-7.57 (m, 2H, ArH), 7.52-7.38 (m, 5H,
ArH, H-4), 6.30-6.19 (m, 1H, H-3), 5.22-5.17 (m, 1H, H-3´), 5.12-4.95 (m, 2H, H-2´, H-4´),
4.70-4.66 (m, 1H, H-2), 4.26-4.12 (m, 2H, H-6´a, H-6´b), 3.73 (m, 2H, H-1´, H-5´), 2.97 (s, 1H,
OH), 2.09 (s, 3H, OAc), 2.06 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.02 (s, 3H, OAc), 1.97-1.89 (m,
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2H, CH2); C NMR (50 MHz, CDCl3 + CCl4) δ 169.5 (2C), 168.7 (2C), 135.3, 134.43, 133.7,
131.3, 128.5, 127.9, 127.4, 125.9, 125.6, 125.4, 123.7 (2C), 76.0, 74.9, 74.0, 71.9, 70.8, 68.5,
62.3, 38.6, 20.5 (2C), 20.4 (2C); ESI-HRMS calcd for C28H32O10Na ([M+Na]+) 551.1888 found
551.1886.
(E)-1-(2´,3´,4´-Tri-O-acetyl-β-D-xylopyranosyl)-2(R/S)-hydroxy-4-phenyl but-3-ene (2i): It
was obtained by the reaction of E-butenoyl-C-glycoside 1i (2.0 g, 4.95 mmol) in methanol (5
mL, 1 M) with CeCl3.6H2O (1.61 g, 4.95 mmol) and NaBH4 (0.18 g, 4.95 mmol) at 0 °C in 95 %
yield (1.90 g) as white solid: mp 122-125 °C; IR (KBr) νmax cm-1: 3438, 1748, 1642, 1220, 773;
1
[α]25 –75.82° (c 0.1, CHCl3); H NMR (300 MHz, CDCl3 + CCl4) δ 7.35-7.23 (m, 5H, ArH),
D
6.63 (d, J = 15.8 Hz, 1H, H-4), 6.23-6.13 (m, 1H, H-3), 5.20-5.10 (m, 1H, H-3´), 5.02-4.94 (m,
1H, H-4´), 4.92-4.84 (m, 1H, H-2´), 4.57-4.49 (m, 1H, H-2), 4.18-4.10 (m, 1H, H-5´a), 3.72-3.33
(m, 1H, H-1´), 3.31-3.24 (m, 1H, H-5´b), 2.75 (s, 1H, OH), 2.05 (s, 3H, OAc), 2.04 (s, 3H, OAc),
13
2.03 (s, 3H, OAc), 1.83-1.71 (m, 2H CH2); C NMR (50 MHz, CDCl3 + CCl4) δ 169.9, 169.4,
169.3, 136.6, 131.9, 130.6, 127.7, 126.4 (2C), 128.5 (2C), 75.2, 73.9, 71.9, 69.4, 68.6, 66.9, 38.7,
20.7 (3C); ESI-HRMS calcd for C21H26O8Na ([M+Na]+) 429.1520 found 429.1520.
(E)-1-(2´,3´,4´-Tri-O-acetyl-β-D-xylopyranosyl)-2(R/S)-hydroxy-4-(4-chlorophenyl)but-3-
ene (2j): It was obtained by the reaction of E-butenoyl-C-glycoside 1j (2.0 g, 4.73 mmol) in
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methanol (5 mL, 0.91 M) with CeCl3.6H2O (1.55 g, 4.73 mmol) and NaBH4 (0.18 g, 4.73 mmol)
at 0 °C in 96 % yield (1.92 g) as white solid: mp 122-125 °C; IR (KBr) νmax cm-1: 3330, 1746,
1627, 1226, 698; [α]25D –69.78° (c 0.1, CHCl3); 1H NMR (300 MHz, CDCl3 + CCl4) δ 7.16 (bs,
4H, ArH), 6.58 (d, J = 15.0 Hz, 1H, H-4), 6.19-6.08 (m, 1H, H-3), 5.19-5.09 (m, 1H, H-3´), 5.01-
4.84 (m, 2H, H-4´, H-2´), 4.55-4.51 (m, 1H, H-2), 4.18-4.11 (m, 1H, H-5´a), 3.70-3.57 (m, 1H,
H-1´), 3.31-3.24 (m, 1H, H-5´b), 2.82 (s, 1H, OH), 2.05 (s, 3H, OAc), 2.04 (s, 3H, OAc), 2.03 (s,
13
3H, OAc), 1.78-1.71 (m, 2H, CH2); C NMR (75 MHz, CDCl3 + CCl4) δ 170.5, 169.6 (2C),
135.2, 133.5, 131.6, 129.4, 128.7 (2C), 127.8 (2C), 76.6, 73.7, 72.0, 71.0, 69.2, 66.9, 38.7, 21.1
(3C); ESI-HRMS calcd for C21H25ClO8Na ([M+Na]+) 463.1130 found 463.1130.
(E)-1-(2´,3´,4´-Tri-O-acetyl-β-D-xylopyranosyl)-2(R/S)-hydroxy-4-(4-flourophenyl)but-3-ene
(2k): It was obtained by the reaction of E-butenoyl-C-glycoside 1k (2.0 g, 4.56 mmol) in
methanol (5 mL, 0.95 M) with CeCl3.6H2O (1.49 g, 4.56 mmol) and NaBH4 (0.17 g, 4.56 mmol)
at 0 °C in 92 % yield (1.84 g) as white solid; mp 122-125 °C; IR (KBr) νmax cm-1: 3438, 1748,
1632, 1220, 769; [α]25 –93.6° (c 0.1, CHCl3); 1H NMR (300 MHz, CDCl3 + CCl4) δ 7.35-7.29
D
(m, 2H, ArH), 7.02-7.96 (m, 2H, ArH), 6.58 (d, J = 15.0 Hz, 1H, H-4), 6.13-6.02 (m, 1H, H-3),
5.19-5.09 (m, 1H, H-3´), 5.01-4.83 (m, 2H, H-4´, H-2´), 4.53-4.47 (m, 1H, H-2), 4.18-4.09 (m,
1H, H-5´a), 3.71-3.52 (m, 1H, H-1´), 3.31-3.24 (t, J = 10.6 Hz, 1H, H-5´b), 2.81 (s, 1H, OH),
2.05 (s, 3H, OAc), 2.04 (s, 3H, OAc), 2.03 (s, 3H, OAc), 1.81-1.69 (m, 2H, CH2); 13C NMR (75
3
MHz, CDCl3 + CCl4) δ 170.3, 169.4 (2C), 132.8, 131.0, 129.4, 128.8, 128.0 (2C, d, JCF = 8.2
2
Hz), 115.0 (2C, d, JCF = 22.1 Hz), 75.3, 72.1, 71.0, 68.9, 66.8, 38.4, 20.6 (3C); ESI-HRMS
calcd for C21H25FO8 ([M+H]+) 425.1790 found 425.1795.
(E)-1-(2´,3´,4´-Tri-O-acetyl-β-D-xylopyranosyl)-2(R/S)-hydroxy-4-(4-methylphenyl)but-3-
ene (2l): It was obtained by the reaction of E-butenoyl-C-glycoside 1l (2.0 g, 4.60 mmol) in
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at 0 °C in 95 % yield (1.90 g) as white solid; mp 152-155 °C; IR (KBr) νmax cm-1: 3556, 1748,
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1641, 1221, 668, 738; [α]25 –77.01° (c 0.1, CHCl3); H NMR (300 MHz, CDCl3) δ 7.27-7.23
D
(m, 2H, ArH), 7.12-7.09 (m, 2H, ArH), 6.58 (d, J2 = 15.0 Hz, 1H, H-4), 6.17-6.10 (m, 1H, H-3),
5.16-5.09 (m, 1H, H-3´), 5.02-4.93 (m, 1H, H-4´), 4.91-4.83 (m, 1H, H-2´), 4.54-4.47 (m, 1H, H-
2), 4.16-4.10 (m, 1H, H-5´a), 3.55-3.48 (m, 1H, H-1´), 3.33-3.26 (m,1H, H-5´b), 2.68 (s, 1H,
OH), 2.35 (s, 3H, CH3), 2.05 (s, 3H, OAc), 2.04 (s, 3H, OAc), 2.03 (s, 3H, OAc), 1.79-1.70 (m,
13
2H, CH2); C NMR (75 MHz, CDCl3) δ 170.8, 170.2, 169.7, 138.1, 133.7, 130.2, 129.0 (2C),
126.6 (3C), 74.1, 72.3, 70.8, 69.3, 66.3, 63.1, 37.8, 21.4, 20.9 (3C); ESI-HRMS calcd for
C22H28O8Na ([M+Na]+) 443.1673 found 443.1679.
(E)-1-(2´,3´,4´-Tri-O-acetyl-β-D-xylopyranosyl)-2(R/S)-hydroxy-4-(4-methoxyphenyl)but-3-
ene (2m): It was obtained by the reaction of E-butenoyl-C-glycoside 1m (2.0 g, 4.78 mmol) in
methanol (5 mL, 0.92 M) with CeCl3.6H2O (1.56 g, 4.78 mmol) and NaBH4 (0.18 g, 4.78 mmol)
at 0 °C in 97 % yield (1.94 g) as white solid; mp 105-110 °C; IR (KBr) νmax cm-1: 3556, 3420,
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1745, 1640, 1224, 778; [α]25 –88.21° (c 0.1, CHCl3); H NMR (300 MHz, CDCl3 + CCl4) δ
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7.31-7.27 (m, 2H, ArH), 6.84-6.56 (m, 2H, ArH), 6.56 (dd, J1 = 2.4 Hz, J2 = 15.8 Hz, 1H, H-4),
6.08-6.01 (m, 1H, H-3), 5.17-5.10 (m, 1H, H-3´), 5.02-4.91 (m, 1H, H-4´), 4.90-4.83 (m, 1H, H-
2´), 4.53-4.46 (m, 1H, H-2), 4.18-4.10 (m, 1H, H-5´a), 3.81 (s, 3H, OCH3), 3.72-3.48 (m, 1H, H-
1´), 3.33-3.24 (m, 1H, H-5´b), 2.64 (s, 1H, OH), 2.05 (s, 3H, OAc), 2.04 (s, 3H, OAc), 2.03 (s,
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3H, OAc), 1.80-1.70 (m, 2H, CH2); C NMR (50 MHz, CDCl3 + CCl4) δ 170.4, 169.6 (2C),
159.5, 130.1, 129.3 (2C),127.3 (2C), 114.1(2C), 73.6, 71.9, 71.2, 69.4 (2C), 66.6, 55.1, 38.9,
20.9 (3C); ESI-HRMS calcd for C22H28O9Na ([M+Na]+) 459.1626 found 459.1629.
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(E)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-mannopyranosyl)-2(R/S)-hydroxy-4-(4-
methylphenyl)but-3-ene (2n): It was obtained by the reaction of E-butenoyl-C-glycoside 1n
(2.0 g, 4.08 mmol) in methanol (5 mL, 0.82 M) with CeCl3.6H2O (1.33 g, 4.08 mmol) and
NaBH4 (0.15 g, 4.08 mmol) at 0 °C in 95 % yield (1.90 g) as white solid: mp 170-173 °C; IR
(KBr) νmax cm-1: 3496, 1744, 1652, 1220, 779; [α]25 –73.42° (c 0.1, CHCl3); H NMR (300
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D
MHz, CDCl3 + CCl4) δ 7.27-7.23 (m, 2H, ArH), 7.09-7.06 (d, J = 7.7 Hz, 2H, ArH), 6.57-6.48
(m, 1H, H-4), 6.16-6.04 (m, 1H, H-3), 5.34-5.28 (m, 1H, H-2´), 5.21-5.11 (m, 1H, H-4´), 4.06-
5.00 (m, 1H, H-3´), 4.42-4.40 (m, 1H, H-2), 4.25-4.06 (m, 2H, H-6´a, H-6´b), 3.97-3.83 (m, 1H,
H-1´), 3.64-3.61 (m, 1H, H-5´), 2.92 (s, 1H, OH), 2.32 (s, 3H, CH3), 2.16 (s, 3H, OAc), 2.08 (s,
13
3H, OAc), 2.03 (s, 3H, OAc), 1.96 (s, 3H, OAc), 1.64-1.52 (m, 2H, CH2); C NMR (50 MHz,
CDCl3 + CCl4) δ 170.4 (2C), 169.8, 169.4, 137.4, 133.7, 130.7, 130.4, 129.6 (2C), 126.4 (2C),
75.7, 73.9, 72.1, 70.6, 69.8, 66.6, 62.8, 37.8, 21.1, 20.6 (4C); ESI-HRMS calcd for C25H32O10Na
([M+Na]+) 515.1888 found 515.1888.
(E)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-mannopyranosyl)-2(R/S)-hydroxy-4-(4-
methoxyphenyl) but-3-ene (2o): It was obtained by the reaction of E-butenoyl-C-glycoside 1o
(2.0 g, 3.93 mmol) in methanol (5 mL, 0.79 M) with CeCl3.6H2O (1.28 g, 3.93 mmol) and
NaBH4 (0.14 g, 3.93 mmol) at 0 °C in 96 % yield (1.92 g) as white solid: IR (Neat) νmax cm-1:
3445, 1763, 1640, 1228, 779; [α]25D –91.74° (c 0.1, CHCl3); 1H NMR (300 MHz, CDCl3) δ 7.33
(d, J = 8.8 Hz, 2H, ArH), 6.88 (d, J = 7.3 Hz, 2H, ArH), 6.85-6.51 (m, 1H, H-4), 6.12-6.02 (m,
1H, H-3), 5.39-5.34 (m, 1H, H-2´), 5.28-5.19 (m, 1H, H-4´), 5.10-5.05 (m, 1H, H-3´), 4.48-4.46
(m, 1H, H-2), 4.28-4.13 (m, 2H, H-6´a, H-6´b), 4.02-3.82 (m, 1H, H-1´), 3.72 (s, 3H, OCH3),
3.71-3.66 (m, 1H, H-5´), 2.90 (s, 1H, OH), 2.19 (s, 3H, OAc), 2.13 (s, 3H, OAc), 2.06 (s, 3H,
13
OAc), 2.00 (s, 3H, OAc), 1.96-1.92 (m, 2H, CH2); C NMR (50 MHz, CDCl3) δ 170.4 (2C),
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169.8, 169.4, 159.3, 137.4, 133.7, 130.1, 127.6 (2C), 113.9 (2C), 75.7, 73.9, 72.1, 70.6, 69.8,
66.6, 62.8, 37.8, 21.1, 20.6 (4C); ESI-HRMS calcd for C25H32O11Na ([M+Na]+) 531.1837 found
531.1827.
General experimental procedure for the synthesis of 1-glycosyl 1,3-dienes (3a-3o)
(EE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-4-(4-fluorophenyl)but-1,3-diene
(3a): To a stirring solution of 1-glycosyl-4-phenyl butene-2-ol 2a (1.0 g, 2.01 mmol) in
anhydrous CH2Cl2 (5 mL, 0.40 M) and Et3N (2.21 mmol) at 0 °C, methanesulfonyl chloride
(0.31 mL, 4.02 mmol) was slowly added. After 15 minutes the stirring reaction mixture was
brought to 40 °C and stirred for 4 hours till the reaction is completed (TLC). The reaction
mixture was evaporated under reduced pressure and extracted by ethyl acetate/water. The ethyl
acetate layer was dried (anhyd. Na2SO4) and evaporated under reduced pressure to give a crude
mass. The latter was purified by column chromatography (SiO2, 60-120 mesh) using hexane:
ethyl acetate (17:3) as eluent to give compound 3a in 68% yield (0.66 g) as a white solid: mp
120-122 °C; IR (KBr) νmax cm-1: 3526, 2901, 1749, 1510, 1228, 774; [α]25 –82.83° (c 0.1,
D
MeOH); 1H NMR (300 MHz, CDCl3 + CCl4) δ 7.36-7.33 (m, 2H, ArH), 7.04-6.99 (m, 2H, ArH),
6.65 (dd, J3,4 = 15.5 Hz, J2,3 = 10.1 Hz, 1H, H-3), 6.58 (d, J = 15.5 Hz, 1H, H-4), 6.43 (dd, J1,2 =
15.2 Hz, J2,3 = 10.1 Hz, 1H, H-2), 5.67 (dd, J1,2 = 15.2 Hz, J1,1´ = 7.5 Hz, 1H, H-1), 5.26 (t, J =
9.4 Hz, 1H, H-3´), 5.11 (t, J = 9.7 Hz, 1H, H-4´), 4.98 (t, J = 9.6 Hz, 1H, H-2´), 4.27 (dd, J6´a,6´b
= 12.2 Hz, J5´,6´a = 4.7 Hz, 1H, H-6´a), 4.15 (dd, J 6´a,6´b = 12.2 Hz, J5´,6´b = 2.0 Hz, 1H, H-6´b),
3.97 (t, J = 7.7 Hz, 1H, H-1´), 3.74 (ddd, J4´,5´ = 9.8 Hz, J5´,6´a = 4.6 Hz, J5´,6´b = 2.2 Hz, 1H, H-5´),
2.10 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.02 (s, 3H, OAc), 1.99 (s, 3H, OAc); 13C NMR (100
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MHz, CDCl3 + CCl4) δ 170.6, 170.2, 169.4, 169.3, 164.60 (d, JCF = 248.6 Hz), 135.1, 133.1,
3
2
132.8, 128.08 (2C, d, JCF = 7.91 Hz), 127.4, 127.2, 115.8 (2C, d, JCF = 22.3 Hz), 79.1, 75.6,
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73.9, 71.4, 68.4, 62.2, 20.8, 20.7, 20.6, 20.5; ESI-HRMS calcd for C24H27FO9Na ([M+Na]+)
501.1531 found 501.1531.
(ZE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-4-(4-fluorophenyl)but-1,3-diene
(3a'): White solid, 10 % yield (0.08 g); mp 118-120 °C; IR (KBr) νmax cm-1: 3481, 2896, 1753,
1
1620, 1228, 779; [α]25 –82.83° (c 0.1, MeOH); H NMR (300 MHz, CDCl3) δ 7.43-7.40 (m,
D
2H, ArH), 7.11-7.01 (m, 2H, ArH), 6.90 (dd, J3,4 = 15.4 Hz, J2,3 = 10.9 Hz, 1H, H-3), 6.60 (d, J =
15.3 Hz, 1H, H-4), 6.33 (t, J = 11.03 Hz, 1H, H-2), 5.39 (dd, J1,2 = 10.5 Hz, J1,1´ = 9.0 Hz, 1H, H-
1), 5.32 (t, J = 9.5 Hz, 1H, H-3´), 5.11 (t, J = 9.8 Hz, 1H, H-4´), 4.98 (t, J = 9.5 Hz, 1H, H-2´),
4.48 (t, J = 9.1 Hz, 1H, H-1´), 4.28 (dd, J6´a,6´b = 12.5 Hz, J5´,6´a = 5.0 Hz, 1H, H-6´a), 4.15 (dd, J
6´a,6´b = 12.3 Hz, J5´,6´b = 2.0 Hz, 1H, H-6´b), 3.79 (ddd, J4´,5´ = 9.8 Hz, J5´,6´a = 4.6 Hz, J5´,6´b = 2.0
13
Hz, 1H, H-5´), 2.07 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.02 (s, 3H, OAc), 1.98 (s, 3H, OAc); C
1
NMR (75 MHz, CDCl3) δ 171.0, 170.7, 169.8 (2C), 164.6 (d, JCF = 251.0 Hz), 134.7, 133.7,
133.2 , 128.5 (2C, d, 3JCF = 7.9 Hz), 126.0, 123.3, 116.0 (2C d, 2JCF = 21.9 Hz), 76.1, 74.9, 74.1,
71.9, 68.7, 62.6, 20.9 (4C); ESI-HRMS calcd for C24H27FO9 ([M+H]+) 479.1712 found
479.1709.
(EE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-4-phenyl but-1,3-diene (3b): It was
obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2b (1.00 g, 2.09 mmol) in anhydrous
CH2Cl2 (5 mL, 0.42 M) at 0-40 °C with Et3N (2.03 mmol) and methanesulfonyl chloride (0.32
mL, 4.18 mmol) in 70 % yield (0.67 g) as white solid: mp 135-137 °C; IR (KBr) νmax cm-1: 3452,
1748, 1640, 1219, 783; [α]25D –7.76° (c 0.1, MeOH); 1H NMR (300 MHz, CDCl3 + CCl4) δ 7.40-
7.37 (m, 2H, ArH), 7.34-7.24 (m, 3H, ArH), 6.74 (dd, J3,4 = 15.1 Hz, J2,3 = 10.3 Hz, 1H, H-3),
6.58 (d, J = 15.4 Hz, 1H, H-4), 6.45 (dd, J1,2 = 15.0 Hz, J2,3 = 10.3 Hz, 1H, H-2), 5.67 (dd, J1,1´
=
7.2 Hz, J1,2 = 15.1 Hz, 1H, H-1), 5.23 (t, J = 9.3 Hz, 1H, H-3´), 5.10 (t, J = 9.8 Hz, 1H, H-4´),
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4.97 (t, J = 9.5 Hz, 1H, H-2´), 4.30 (dd, J6´a,6´b = 12.4 Hz, J5´,6´a = 4.8 Hz, 1H, H-6´a), 4.15 (dd,
J6´a,6´b = 12.5 Hz, J5´,6´b = 2.0 Hz, 1H, H-6´b), 3.96 (t, J = 8.2 Hz, 1H, H-1´), 3.73-3.71 (m, 1H, H-
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5´), 2.12 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.03 (s, 3H, OAc), 2.00 (s, 3H, OAc); C NMR (50
MHz, CDCl3 + CCl4) δ 170.3, 170.0, 169.1 (2C), 135.2, 134.4 (2C), 128.6 (2C), 128.0, 127.4
(2C), 126.5 (2C), 79.2, 75.7, 73.9, 71.4, 68.4, 62.1, 20.7, 20.6, 20.5 (2C); ESI-HRMS calcd for
C24H28O9Na ([M+Na]+) 483.1626 found 483.1624.
(EE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-4-(4-bromophenyl)but-1,3-diene
(3c): It was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2c (1.00 g, 1.79 mmol)
in anhydrous CH2Cl2 (5 mL, 0.36 M) at 0-40 °C with Et3N (2.15 mmol), methanesulfonyl
chloride (0.3 mL, 3.58 mmol) in 69 % yield (0.66 g) as white solid: mp 142-145 °C; IR (KBr)
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νmax cm-1: 3543, 2892, 1748, 1640, 1246, 1047, 773; [α]25 –69.70° (c 0.1, MeOH); H NMR
D
(300 MHz, CDCl3 + CCl4) δ 7.29 (m, 2H, ArH), 7.26 (d, J = 7.7 Hz, 2H, ArH), 6.70 (dd, J3,4
=
15.4 Hz, J2,3 = 10.4 Hz, 1H, H-3), 6.57 (d, 1H, J3,4 = 15.5 Hz, 1H, H-4), 6.43 (dd, J1,2 = 15.1 Hz,
J2,3 = 10.4 Hz, 1H, H-2), 5.63 (dd, J1,2 = 15.0 Hz, J1,1´ = 7.4 Hz, 1H), 5.23 (t, J = 9.4 Hz, 1H, H-
3´), 5.09 (t, J = 9.7 Hz, 1H, H-4´), 4.97 (t, J = 9.6 Hz, 1H, H-2´), 4.27 (dd, J6´a,6´b = 12.3 Hz,
J5´,6´a = 4.9 Hz, 1H, H-6´a), 4.12 (d, J = 12.1 Hz, 1H, H-6´b), 3.95 (t, J = 7.9 Hz, 1H, H-1´), 3.73
13
(m, 1H, H-5´), 2.10 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.02 (s, 3H, OAc), 1.99 (s, 3H, OAc); C
NMR (50 MHz, CDCl3 + CCl4) δ 170.4, 170.1, 169.2 (2C), 137.8, 135.5, 134.4, 133.8, 129.3
(3C), 126.7, 126.5 (2C), 79.2, 75.6, 73.9, 71.5, 68.4, 62.1, 20.6 (4C); ESI-HRMS calcd for
C24H27BrO9Na ([M+Na]+) 561.0836 found 561.0835.
(EE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-4-(4-chlorophenyl)but-1,3-diene
(3d): It was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2d (1.00 g, 1.95 mmol)
in anhydrous CH2Cl2 (5 mL, 0.39 M) at 0-40 °C with Et3N (2.15 mmol) and methanesulfonyl
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chloride (0.3 mL, 3.90 mmol) in 69 % yield (0.67 g) as white solid: mp 138-140 °C; IR (KBr)
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νmax cm-1: 3410, 2889, 1743, 1680, 1238, 791; [α]25 –129.16° (c 0.1, CHCl3); H NMR (300
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MHz, CDCl3 + CCl4) δ 7.30 (bs, 4H, ArH), 6.71 (dd, J3,4 = 15.4 Hz, J2,3 = 10.5 Hz, 1H, H-3),
6.53 (d, J = 15.6 Hz, 1H, H-4), 6.44 (dd, J1,2 = 15.1 Hz, J2,3 = 10.7 Hz, 1H, H-2), 5.69 (dd, J1,2 =
15.0 Hz, J1,1´ = 7.4 Hz, 1H, H-1), 5.25 (t, J = 9.3 Hz, 1H, H-3´), 5.15 (t, J = 9.7 Hz, 1H, H-4´),
4.98 (t, J = 9.5 Hz, 1H, H-2´), 4.27 (dd, J6´a,6´b = 12.2 Hz, J5´,6´a = 4.5 Hz, 1H, H-6´a), 4.14 (d, J =
12.2 Hz, 1H, H-6´b), 3.97 (t, J = 8.0 Hz, 1H, H-1´), 3.74 (ddd, J4´,5´ = 9.6 Hz, J5´,6´a = 4.2 Hz,
J5´,6´b = 2.3 Hz, 1H, H-5´), 2.10 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.02 (s, 3H, OAc), 1.99 (s, 3H,
OAc); 13C NMR (50 MHz, CDCl3 + CCl4) δ 170.3, 170.0, 169.1 (2C), 135.1, 134.7, 133.7, 133.0,
128.8 (2C), 128.0, 128.01, 127.6 (2C), 78.9, 75.7, 73.9, 71.4, 68.4, 62.1, 20.7, 20.6, 20.6, 20.5;
ESI-HRMS calcd for C24H27ClO9Na ([M+Na]+) 517.1236 found 517.1236.
(EE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-4-(2-chlorophenyl)but-1,3-diene
(3e): It was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2e (1.00 g, 1.95 mmol)
in anhydrous CH2Cl2 (5 mL, 0.39 M) at 0-40 °C with Et3N (2.01 mmol) and methanesulfonyl
chloride (0.3 mL, 3.80 mmol) 66 % yield (0.63 g) as white solid: mp 130-132 °C; IR (KBr) νmax
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cm-1: 3424, 2910, 1753, 1689, 1232, 669; [α]25 –57.9° (c 0.1, CHCl3); H NMR (300 MHz,
D
CDCl3) δ 7.36 (s, 1H, ArH), 7.27-7.21 (m, 3H, ArH), 6.76 (m, 1H, H-3), 6.53 (d, J = 15.9 Hz,
1H, H-4), 6.44-6.39 (m, 1H, H-2), 5.72 (dd, J1,2 = 15.1 Hz, J1,1´ = 7.4 Hz, 1H, H-1), 5.25 (t, J =
9.4 Hz, 1H, H-3´), 5.11 (t, J = 9.8 Hz, 1H, H-4´), 4.97 (t, J = 9.6 Hz, 1H, H-2´), 4.28 (dd, J6´a,6´b
= 12.4 Hz, J5´,6´a = 4.7 Hz, 1H, H-6´a), 4.16 (d, J = 12.2 Hz, 1H, H-6´b), 3.97 (m, 1H, H-1´), 3.74
(ddd, J4´,5´ = 9.9 Hz, J5´,6´a = 4.6 Hz, J5´,6´b = 2.1 Hz, 1H, H-5´), 2.10 (s, 3H, OAc), 2.04 (s, 3H,
OAc), 2.01 (s, 3H, OAc), 1.99 (s, 3H, OAc); 13C NMR (50 MHz, CDCl3) δ 170.7, 170.3, 169.5,
169.4, 138.6, 134.7, 134.6, 132.8, 129.8, 128.8, 128.5, 127.8, 126.5, 124.7, 78.9, 75.7, 73.9, 71.5,
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68.5, 62.3, 20.7, 20.6, 20.6, 20.5; ESI-HRMS calcd for C24H27ClO9Na ([M+Na]+) 517.1236
found 517.1237.
(EE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-4-(4-isopropylphenyl)but-1,3-diene
(3f): It was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2f (1.00 g, 1.92 mmol)
in anhydrous CH2Cl2 (5 mL, 0.38 M) at 0-40 °C with Et3N (2.11 mmol) and methanesulfonyl
chloride (0.3 mL, 3.84 mmol) in 67 % yield (0.64 g) as white solid: mp 92-95 °C; IR (KBr) νmax
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cm-1: 3407, 2849, 2496, 1689, 1460, 1220, 694; [α]25 –7.15° (c 0.1, CHCl3); H NMR (300
D
MHz, CDCl3 + CCl4) δ 7.30 (d, J = 8.1 Hz, 2H, ArH), 7.18 (d, J = 8.0 Hz, 2H, ArH), 6.71 (dd,
J3,4 = 15.5 Hz, J2,3 = 10.3 Hz, 1H, H-3), 6.58 (d, J = 15.6 Hz, 1H, H-4), 6.44 (dd, J1,2 = 15.0 Hz,
J2,3 = 10.3 Hz, 1H, H-2), 5.65 (dd, J1,2 = 15.0 Hz, J1,1´ = 7.6 Hz, 1H, H-1), 5.23 (t, J = 9.4 Hz, 1H,
H-3´), 5.10 (t, J = 9.7 Hz, 1H, H-4´), 4.97 (t, J = 9.6 Hz, 1H, H-2´), 4.29 (dd, J6´a,6´b = 12.5 Hz,
J5´,6´a = 4.9 Hz, 1H, H-6´a), 4.14 (dd, J 6´a,6´b = 12.3 Hz, J5´,6´b = 1.6 Hz, 1H, H-6´b), 3.95 (t, J =
8.0 Hz, 1H, H-1´), 3.74-3.70 (m, 1H, H-5´), 2.95-2.86 (m, 1H, CH), 2.11 (s, 3H, OAc), 2.05 (s,
13
3H, OAc), 2.03 (s, 3H, OAc), 1.99 (s, 3H, OAc), 1.27 (m, 6H, 2×CH3); C NMR (50 MHz,
CDCl3 + CCl4) δ 170.2 (2C), 169.4 (2C), 149.0, 136.4 (2C), 135.4 (2C), 134.5, 134.3, 126.4
(3C), 79.2, 75.7, 73.9, 71.5, 69.5, 62.3, 33.9, 23.9 (2C), 20.6 (4C); ESI-HRMS calcd for
C27H34O9Na ([M+Na]+) 525.2095 found 525.2095.
(EE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-4-(4-methoxyphenyl)but-1,3-diene
(3g): It was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2g (1.00 g, 1.96 mmol)
in anhydrous CH2Cl2 (5 mL, 0.39 M) at 0-40 °C with Et3N (2.16 mmol) and methanesulfonyl
chloride (0.3 mL, 3.92 mmol) as described above in 76 % yield (0.78 g) as a white solid: mp
110-112 °C; IR (KBr) νmax cm-1: 3368, 2890, 1745, 1652, 1234, 698; [α]25 –51.02° (c 0.1,
D
MeOH); 1H NMR (300 MHz, CDCl3 + CCl4) δ 7.35-7.30 (m, 2H, ArH), 6.85-6.82 (m, 2H, ArH),
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6.56-6.53 (m, 1H, H-3), 6.45 (d, J = 15.3 Hz, 1H, H-4), 6.41 (dd, J1,2 = 15.0 Hz, J2,3 = 10.0 Hz,
1H, H-2), 5.63 (dd, J1,2 = 15.0 Hz, J1,1´ = 7.6 Hz, 1H, H-1), 5.22 (t, J = 9.4 Hz, 1H, H-3´), 5.09 (t,
J = 9.7 Hz, 1H, H-4´), 4.96 (t, J = 9.5 Hz, 1H, H-2´), 4.27 (dd, J6´a,6´b = 12.3 Hz, J5´,6´a = 4.7 Hz,
1H, H-6´a), 4.11 (d, J = 12.2 Hz, 1H, H-6´b), 3.93 (t, J = 8.8 Hz, 1H, H-1´), 3.81 (s, 3H, OCH3),
3.73-3.69 (m, 1H, H-5´), 2.10 (s, 3H, OAc), 2.04 (s, 3H, OAc), 2.01 (s, 3H, OAc), 1.99 (s, 3H,
OAc); 13C NMR (50 MHz, CDCl3 + CCl4) δ 170.4, 169.9, 169.2 (2C), 159.5, 135.7, 134.0,
129.4, 127.8 (2C), 126.2, 125.3, 114.2 (2C), 79.3, 75.8, 74.1, 71.6, 68.4, 62.3, 55.2, 20.7, 20.6
(3C); ESI-HRMS calcd for C25H30O10Na ([M+Na]+) 513.1731 found 513.1732.
(EE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-glucopyranosyl)-4-(2-naphathalenyl)but-1,3-diene
(3h): It was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2h (1.00 g, 1.92 mmol)
in anhydrous CH2Cl2 (5 mL, 0.38 M) at 0-40 °C with Et3N (2.11 mmol) and methanesulfonyl
chloride (0.3 mL, 3.94 mmol) in 74 % yield (0.71 g) as white solid: mp 112-115 °C; IR (KBr)
1
νmax cm-1: 3435, 1759, 1641, 1220, 772; [α]25 –25.81° (c 0.1, CHCl3); H NMR (300 MHz,
D
CDCl3 + CCl4) δ 8.12 (d, J = 7.3 Hz, 1H, ArH), 7.86-7.83 (m, 1H, ArH), 7.79 (d, J = 8.1 Hz, 1H,
ArH), 7.65 (d, J = 7.0 Hz, 1H, ArH), 7.54-7.42 (m, 3H, ArH), 6.39 (d, J = 15.3 Hz, 1H, H-4),
6.82 (dd, J3,4 = 15.1 Hz, J2,3 = 10.6 Hz, 1H, H-3), 6.65 (dd, J1,2 = 15.0 Hz, J2,3 = 10.7 Hz, 1H, H-
2), 5.74 (dd, J1,2 = 15.0 Hz, J1,1´ = 7.3 Hz, 1H, H-1), 5.26 (t, J = 9.4 Hz, 1H, H-3´), 5.12 (t, J = 9.7
Hz, 1H, H-4´), 5.01 (t, J = 9.6 Hz, 1H, H-2´), 4.30 (dd, J6´a,6´b = 12.4 Hz, J5´,6´a = 4.7 Hz, 1H, H-
6´a), 4.15 (dd, J6´a,6´b = 12.3 Hz, J5´,6´b = 2.0 Hz, 1H, H-6´b), 4.01 (t, J = 7.8 Hz, 1H, H-1´), 3.75
(ddd, J4´,5´ = 9.8 Hz, J5´,6´a = 4.5 Hz, J5´,6´b = 2.5 Hz, 1H, H-5´), 2.13 (s, 3H, OAc), 2.06 (s, 3H,
OAc), 2.04 (s, 3H, OAc), 2.03 (s, 3H, OAc); 13C NMR (50 MHz, CDCl3 + CCl4) δ 170.4, 170.1,
169.2 (2C), 135.4, 133.9, 133.7, 131.2, 131.1, 130.2, 128.6, 128.4, 127.7 (2C), 126.1, 125.5,
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123.6, 123.4, 79.0, 75.7, 73.9, 71.5, 68.4, 62.2, 20.7, 20.6, 20.6, 20.5; ESI-HRMS calcd for
C28H30O9 ([M+H]+) 511.1962 found 511.1962.
(EE)-1-(2´,3´,4´-Tri-O-acetyl-β-D-xylopyranosyl)-4-phenyl but-1,3-diene (3i): It was obtained
by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2i (1.00 g, 2.57 mmol) in anhydrous CH2Cl2
(5 mL, 0.49 M) at 0-40 °C with Et3N (2.83 mmol), methanesulfonyl chloride (0.4 mL, 5.14
mmol) in 76 % yield (0.78 g) as white solid: mp 122-125 °C; IR (KBr) νmax cm-1: 3298, 1743,
1650, 1220, 679; [α]25D –26.18° (c 0.1, CHCl3); 1H NMR (300 MHz, CDCl3 + CCl4) δ 7.39-7.20
(m, 5H, ArH), 6.74 (dd, J3,4 = 15.6 Hz, J2,3 = 10.5 Hz, 1H, H-3), 6.56 (d, J = 15.6 Hz, 1H, H-4),
6.45 (dd, J1,2 = 15.1 Hz, J2,3 = 10.5 Hz, 1H, H-2), 5.66 (dd, J1,2 = 15.1 Hz, J1,1´ = 7.2 Hz, 1H, H-
1), 5.22 (t, J = 9.4 Hz, 1H, H-3´), 5.07-4.98 (m, 1H, H-4´), 4.17 (t, J = 9.5 Hz, 1H, H-2´), 4.16
(dd, J4´,5´a = 5.6 Hz, J5´a,5´b = 11.1 Hz, 1H, H-5´a), 3.87 (t, J = 7.6 Hz, 1H, H-1´), 3.34 (t, J = 11.1
13
Hz, 1H, H-5´b), 2.05 (s, 3H, OAc), 2.04 (s, 3H, OAc), 1.99 (s, 3H, OAc); C NMR (50 MHz,
CDCl3 + CCl4) δ 170.0, 169.5, 169.3, 136.7, 134.9, 134.3, 128.6 (2C), 127.9, 127.7, 127.5, 126.6
(2C), 79.6, 73.6, 71.8, 69.3, 66.7, 20.7 (3C); ESI-HRMS calcd for C21H24O7Na ([M+Na]+)
411.1414 found 411.1413.
(EE)-1-(2´,3´,4´-Tri-O-acetyl-β-D-xylopyranosyl)-4-(4-chlorophenyl)but-1,3-diene (3j): It
was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2j (1.00 g, 2.27 mmol) in
anhydrous CH2Cl2 (5 mL, 0.45 M) at 0-40 °C with Et3N (2.16 mmol) and methanesulfonyl
chloride (0.35 mL, 4.54 mmol) in 76 % yield (0.78 g) as white solid: mp 142-145 °C; IR (KBr)
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νmax cm-1: 3248, 1748, 1649, 1217, 771; [α]25 –43.18° (c 0.1, CHCl3); H NMR (300 MHz,
D
CDCl3 + CCl4) δ 7.33-7.30 (m, 4H, ArH), 6.72 (dd, J3,4 = 15.5 Hz, J2,3 = 10.5 Hz, 1H, H-3), 6.51
(d, J = 15.7 Hz, 1H, H-4), 6.44 (dd, J2,3 = 10.7 Hz, J1,2 = 15.4 Hz, 1H, H-2), 5.67 (dd, J1,2 = 15.2
Hz, J1,1´ = 7.3 Hz, 1H, H-1), 5.25 (t, J = 9.5 Hz, 1H, H-3´), 5.06-5.01 (m, 1H, H-4´), 4.92 (t, J =
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9.6 Hz, 1H, H-2´), 4.18 (dd, J4´,5´a = 5.6 Hz, J5´a,5´b = 11.2 Hz, 1H, H-5´a), 3.89 (t, J = 7.8 Hz, 1H,
H-1´), 3.36 (t, J = 11.0 Hz, 1H, H-5´b), 2.05 (s, 3H, OAc), 2.04 (s, 3H, OAc), 2.00 (s, 3H, OAc);
13C NMR (50 MHz, CDCl3 + CCl4) δ 170.3, 169.7, 169.5, 135.2, 134.6, 133.6, 132.9, 128.8 (2C),
128.4, 128.1, 127.7 (2C), 79.5, 73.5, 71.8, 69.3, 66.7, 20.7 (3C); ESI-HRMS calcd for
C21H23ClO7Na ([M+Na]+) 445.1025 found 445.1025.
(EE)-1-(2´,3´,4´-Tri-O-acetyl-β-D-xylopyranosyl)-4-(4-fluorophenyl)but-1,3-diene (3k): It
was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2k (1.00 g, 2.45 mmol) in
anhydrous CH2Cl2 (5 mL, 0.47 M) at 0-40 °C with Et3N (2.70 mmol) and methanesulfonyl
chloride (0.38 mL, 4.90 mmol) in 76 % yield (0.78 g) as white solid: mp 105-107 °C; IR (KBr)
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νmax cm-1: 3543, 1748, 1640, 1246, 1047, 798; [α]25 –93.64° (c 0.1, CHCl3); H NMR (300
D
MHz, CDCl3) δ 7.37-7.33 (m, 2H, ArH), 7.03-6.97 (m, 2H, ArH), 6.65 (dd, J3,4 = 15.5 Hz J2,3
=
10.3 Hz, 1H, H-3), 6.54 (d, J = 15.6 Hz, 1H, H-4), 6.42 (dd, J1,2 = 15.2 Hz, J2,3 = 10.4 Hz, 1H, H-
2), 5.65 (dd, J1,2 = 15.0 Hz, J1,1´ = 7.2 Hz, 1H, H-1), 5.22 (t, J = 9.5 Hz, 1H, H-3´), 5.06-4.98 (m,
1H, H-4´), 4.93 (t, J = 9.6 Hz, 1H, H-2´), 4.16 (dd, J4´,5´a = 5.6 Hz, J5a´,5´b = 11.1 Hz, 1H, H-5´a),
3.86 (t, J = 7.7 Hz, 1H, H-1´), 3.34 (t, J = 11.0 Hz, 1H, H-5´b), 2.05 (s, 3H, OAc), 2.04 (s, 3H,
13
1
OAc), 1.99 (s, 3H, OAc); C NMR (75 MHz, CDCl3) δ 170.3, 169.8, 169.6, 164.2 (d, JCF
=
=
251.6 Hz), 134.9, 133.0, 132.9, 128.4 (2C, d, 3JCF = 7.9 Hz), 127.7, 127.3, 116.0 (2C, d, JCF
2
21.9 Hz), 79.5, 73.5, 71.8, 69.3, 66.7, 20.7 (3C); ESI-HRMS calcd for C21H23FO7Na ([M+Na]+)
429.1350 found 429.1352.
(EE)-1-(2´,3´,4´-Tri-O-acetyl-β-D-xylopyranosyl)-4-(4-methylphenyl)but-1,3-diene (3l): It
was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2l (1.00 g, 2.48 mmol) in
anhydrous CH2Cl2 (5 mL, 0.48 M) at 0-40 °C with Et3N (2.73 mmol) and methanesulfonyl
chloride (0.38 mL, 4.96 mmol) in 76 % yield (0.78 g) as white solid: mp 152-155 °C; IR (KBr)
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νmax cm-1: 3483, 1754, 1643, 1223, 1045, 771; [α]25 – 76.82° (c 0.1, CHCl3); H NMR (300
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MHz, CDCl3 + CCl4) δ 7.29-7.27 (m, 2H, ArH), 7.13 (d, J = 7.8 Hz, 2H, ArH), 6.70 (dd, J3,4
15.5 Hz, J2,3 = 10.3 Hz, 1H, H-3), 6.56 (d, J = 15.5 Hz, 1H, H-4), 6.44 (dd, J1,2 = 15.1 Hz, J2,3
=
=
10.5 Hz, 1H, H-2), 5.62 (dd, J1,1´ = 7.3 Hz, J1,2 = 15.1 Hz, 1H, H-1), 5.25 (t, J = 9.4 Hz, 1H, H-
3´), 5.07-5.00 (m, 1H, H-4´), 4.90 (t, J = 9.6 Hz, 1H, H-2´), 4.15 (dd, J4´,5´a = 5.6 Hz, J5a´,5´b
=
11.1 Hz, 1H, H-5´a), 3.87 (t, J = 7.8 Hz, 1H, H-1´), 3.35 (t, J = 11.0 Hz, 1H, H-5´b), 2.35 (s, 3H,
13
CH3), 2.06 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.01 (s, 3H, OAc); C NMR (50 MHz, CDCl3 +
CCl4) δ 170.1, 169.5, 169.3, 137.7, 135.2, 134.3, 133.9, 129.3 (2C), 127.0 (2C), 126.5 (2C), 79.6,
73.5, 71.8, 69.3, 66.6, 21.2, 20.7 (3C); ESI-HRMS calcd for C22H26O7Na ([M+Na]+) 425.1571
found 425.1569.
(EE)-1-(2´,3´,4´-Tri-O-acetyl-β-D-xylopyranosyl)-4-(4-methoxyphenyl)but-1,3-diene (3m):
It was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2m (1.00 g, 2.39 mmol) in
anhydrous CH2Cl2 (5 mL, 0.46 M) at 0-40 °C with Et3N (2.63 mmol) and methanesulfonyl
chloride (0.44 mL, 5.78 mmol) in 76 % yield (0.78 g) as white solid: mp 115-117 °C; IR (KBr)
νmax cm-1: 3520, 1748, 1629, 1213, 773; [α]25 –40.99° (c 0.1, CHCl3); H NMR (300 MHz,
1
D
CDCl3) δ 7.38-7.30 (m, 2H, ArH), 6.89-6.82 (m, 2H, ArH), 6.62 (dd, J 2,3 = 10.3 Hz, J3,4 = 15.4
Hz, 1H, H-3), 6.53 (d, J = 15.5 Hz, 1H, H-4), 6.41 (dd, J2,3 = 10.3 Hz, J1,2 = 15.0 Hz, 1H, H-2),
5.61 (dd, J1,1´ = 7.4 Hz, J1,2 = 15.0 Hz, 1H, H-1), 5.22 (t, J = 9.5 Hz, 1H, H-3´), 5.06-4.98 (m, 1H,
H-4´), 4.90 (t, J = 9.5 Hz, 1H, H-2´), 4.16 (dd, J4´,5´a = 5.6 Hz, J5´a,5´b = 11.1 Hz, 1H, H-5´a), 3.83
(m, 4H, H-1´, OCH3), 3.34 (t, J = 10.8 Hz, 1H, H-5´b), 2.05 (s, 3H, OAc), 2.04 (s, 3H, OAc),
1.99 (s, 3H, OAc); 13C NMR (50 MHz, CDCl3) δ 170.4, 169.8, 169.7, 159.6, 135.5, 133.9, 134.3,
129.6, 128.0, 127.8, 126.5, 125.5, 114.2, 79.8, 73.5, 71.8, 69.4, 66.6, 55.3, 20.7 (3C); ESI-
HRMS calcd for C22H26O8 ([M+H]+) 419.1685 found 419.1689.
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(EE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-mannopyranosyl)-4-(4-methylphenyl)but-1,3-diene
(3n): It was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2n (1.00 g, 2.03 mmol)
in anhydrous CH2Cl2 (5 mL, 0.41 M) at 0-40 °C with Et3N (2.23 mmol) and methanesulfonyl
chloride (0.3 mL, 4.06 mmol) in 74 % yield (0.71 g) as white solid: mp 118-120 °C; IR (KBr)
νmax cm-1: 3410, 1754, 1631, 1210, 774; [α]25D –105° (c 0.1, CHCl3); 1H NMR (300 MHz, CDCl3
+ CCl4) δ 7.54-7.43 (m, 2H, ArH), 7.36-7.31 (m, 2H, ArH), 6.69 (dd, J2,3 = 10.4 Hz, J3,4 = 15.4
Hz, 1H, H-3), 6.58 (d, J = 15.5 Hz, 1H, H-4), 6.48 (dd, J2,3 = 10.3 Hz, J1,2 = 15.2 Hz, 1H, H-2),
5.65 (dd, J1,2 = 15.2 Hz, J1,1´ = 5.7 Hz, 1H, H-1), 5.45 (d, J = 2.3 Hz, 1H, H-2´), 5.30 (t, J = 10.0
Hz, 1H, H-4´), 5.13 (t, J = 9.9 Hz, 1H, H-3´), 4.31 (m, 2H, H-1´ + H-6´a), 4.20 (d, J = 12.1 Hz,
1H, H-6´b), 3.79-3.71 (m, 1H, H-5´), 2.34 (s, 3H, CH3), 2.12 (s, 3H, OAc), 2.09 (s, 3H, OAc),
2.04 (s, 3H, OAc), 2.01 (s, 3H, OAc); 13C NMR (50 MHz, CDCl3 + CCl4) δ 170.7, 170.4, 170.1,
169.6, 137.8, 134.0, 133.9, 129.4 (2C), 126.7, 126.4 (2C), 126.0 (2C), 77.6, 76.2, 72.3, 70.1,
66.0, 62.9, 21.3, 20.8, 20.7, 20.6 (2C); ESI-HRMS calcd for C25H30O9Na ([M+Na]+) 497.1782
found 497.1783.
(EE)-1-(2´,3´,4´,6´-Tetra-O-acetyl-β-D-mannopyranosyl)-4-(4-methoxylphenyl)but-1,3-diene
(3o): It was obtained by the reaction of 1-glycosyl-4-phenyl butene-2-ol 2o (1.00 g, 1.96 mmol)
in anhydrous CH2Cl2 (5 mL, 0.39 M) at 0-40 °C with Et3N (2.34 mmol) and methanesulfonyl
chloride (0.3 mL, 3.92 mmol) in 75 % yield (0.76 g) as white solid: mp 118-120 °C; IR (KBr)
1
νmax cm-1: 3410, 1754, 1631, 1210, 774; [α]25 –56.2° (c 0.1, CHCl3); H NMR (300 MHz,
D
CDCl3) δ 7.39-7.33 (m, 2H, ArH), 6.89-6.86 (m, 2H, ArH), 6.66-6.55 (m, 2H, H-3, H-4), 6.52
(dd, J2,3 = 10.2 Hz, J1,2 = 15.5 Hz, 1H, H-2), 5.66 (dd, J1,2 = 14.9 Hz, J1,1´ = 5.7 Hz, 1H, H-1),
5.46 (d, J = 3.2 Hz, 1H, H-2´), 5.34- 5.27 (m, 1H, H-4´), 5.15 (dd, J2´,3´ = 3.3 Hz, J3´,4´ = 10.1 Hz,
1H, H-3´), 4.35-4.29 (m, 2H, H-6´a, H-1´), 4.23 (dd, J5´,6´b = 2.2 Hz, J 6´a,6´b = 12.2 Hz, 1H, H-
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