First total chemical synthesis of natural acyl derivatives of some phenolglycosides of the family Salicaceae

Article abstract of DOI:10.1016/j.carres.2012.10.006

The total synthesis of certain natural phenolglycosides of the family Salicaceae, namely: salireposide, populosides A, B, and C and not occurring in plants desoxysalireposide (2-(β-d-glucopyranosyloxy)-benzylbenzoate) and per-acetate of iso-salireposide (2-(β-d-glucopyranosyloxy)-5-benzoyloxy benzyl alcohol), starting from readily available phenols and glucose was accomplished. A simple method for the synthesis of phenolglycosides derivatives of 2-acyloxy salicyl and gentisyl alcohol was developed. The key step of these natural products' synthesis is a selective removal of acetyl groups in the presence of other acyl groups.

Full text of DOI:10.1016/j.carres.2012.10.006

Accepted Manuscript
First total chemical synthesis of natural acyl derivatives of some phenolglyco‐
sides of the family Salicaceae
Maxim L. Belyanin, Elena V. Stepanova, Vladimir D. Ogorodnikov
PII:
S0008-6215(12)00419-3
DOI:
http://dx.doi.org/10.1016/j.carres.2012.10.006
CAR 6308
Reference:
To appear in:
Carbohydrate Research
Received Date:
Revised Date:
Accepted Date:
8 June 2012
3 October 2012
5 October 2012
Please cite this article as: Belyanin, M.L., Stepanova, E.V., Ogorodnikov, V.D., First total chemical synthesis of
natural acyl derivatives of some phenolglycosides of the family Salicaceae, Carbohydrate Research (2012), doi:
http://dx.doi.org/10.1016/j.carres.2012.10.006
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First total chemical synthesis of natural acyl derivatives of some phenolglycosides of the
family Salicaceae
Maxim L. Belyanina, Elena V. Stepanova*a, Vladimir D. Ogorodnikovb
aNational Research Tomsk Polytechnic University, 30 Lenin Avenue, Tomsk, 634050,
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Russia.
b The Institute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Science,
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4 Akademichesky Avenue, 634021, Tomsk, Russia
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Abstract
The total synthesis of certain natural phenolglycosides of the family Salicaceae, namely:
salireposide, populosides A, B, and C and not occurring in plants desoxysalireposide (2-(β-D-
glucopyranosyloxy)-benzylbenzoate)
and
per-acetate
of
iso-salireposide
(2-(β-D-
glucopyranosyloxy)-5-benzoyloxy benzyl alcohol), starting from readily available phenols and
glucose was accomplished. A simple method for the synthesis of phenolglycosides derivatives of
2-acyloxy salicyl and gentisyl alcohol was developed. The key step of these natural products
synthesis is a selective removal of acetyl groups in the presence of other acyl groups.
Key Words
Phenolic glycosides, glycosylation, salireposide, populosides A, B, C, protective groups
cleavage
* Corresponding author. Present address: National Research Tomsk Polytechnic University,
30 Lenin Avenue, Tomsk, 634050, Russia.
Tel.: 8 (3822) 56-38-61, Fax: 8 (3822) 56-36-37, e-mail: eline_m@mail.ru
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1. Introduction
Phenolglycosides derivatives of 2-acyloxy salicyl alcohol are widespread in plants of the
family Salicaceae. Most phenolglycosides of this family contain salicin moiety (2-(β-D-
glucopyranosyloxy)-benzyl alcohol). These natural compounds cover a large spectrum of
biological activity. Phenolic glycosides are some of the most abundant secondary metabolites
known in plant tissues, and play an important role as anti-herbivore defenses in the Salicaceae1,2.
Salireposide (1) has antiviral activity3, antitumor activity4,5. It could be useful for the arthritis
therapy5 and shows an inhibitory activity against snake-venom phosphodiesterase6. Populosides
A (2), B (3) and C (4) exhibit antioxidant activity7. These compounds are also potential
candidates for acute or chronic opisthorchiasis treatment.
Salireposide was found out in many plants8-13. Populosides A, B, C were first isolated from
Populus davidiana in 20067, and populoside A was also isolated from P. ussuriensis14.
However, despite the fact that phenolglycosides, derivatives of 2-acyloxy salicyl alcohol are
well-known as natural compounds, there is no mentioning on the synthesis of these glycosides in
the literature to date. Thus, the present work aim is to synthesize some phenolglycosides
inaccessible from natural sources (Fig. 1.).
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Figure 1. Structure of synthesized phenolglycosides
It was found that salireposide (1) cannot be selectively obtained by direct benzoylation of
salirepin (2-(β-D-glucopyranosyloxy)-5-hydroxy benzyl alcohol), since a mixture of acylated
products was formed. In addition, it is known that benzoylation of glycosides firstly goes to the
C-6 hydroxygroup of the glucose residue15,16 rather than alcohol hydroxyl of the aglycone.
The present paper reports on the first synthesis of salireposide and 2-acyl analogs of salicin
and salirepin: populosides A, B, C, desoxysalireposide and per-acetate of artifical iso-
salireposide – 4-benzoyloxy-salicin. The suggested method allows to obtain phenolglycosides,
derivatives of 2-acyloxy salicyl alcohol in a selective way.
2. Results and Discussion
Salicylic aldehyde (5) or 4-O-acetyloxy salicylic aldehyde (6a) and 4-O-benzoyloxy salicylic
aldehyde (6b) were used as initial substrates (Scheme 1.). Aldehydes 6a, 6b were obtained by
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selective formylation of monoacyl-hydroquinone (7a,7b), which in turn can be easily obtained
by hydroquinone acylation17.
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α-D-acetobromglucose (ABG) was employed as a donor of a carbohydrate residue in the
glycosylation reaction. Glycosylation of 5 was carried out under Koennigs-Knorr conditions in
aqueous acetone with an equimolar amount of NaOH18 to produce glycoside 8. Unfortunately,
this method proved to be unsuited for 6a and 6b glycosylation, since acyl group of the aglycone
was removed and, consequently, several isomeric glycosides were formed. Therefore, for 6a and
6b glycosylation another way for Koennigs-Knorr method was applied. This method avoids the
aquatic environment, using quinoline and silver oxide. Although a number of side-reactions take
place19, glycosides 9 and 10, respectively, were obtained by higher yields rather than employing
aqueous acetone. Both methods produce glycosides of β-configuration.
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Scheme 1. Synthesis of 2-acyl phenolglycosides.
Reagents and conditions: (a) Ac2O, AcOH, 2h, 110°C; (b) BzCl, NaOH, H2O 1h 40 min, 5°C; (c) CF3COOH,
hexamethylentetramine, 1h, 80°C; (d) Acetobromglucose, NaOH, acetone 24h, 20°C; (e) Acetobromglucose, Ag2O, quinoline,
1h, 20°C; (f) NaBH4, CTMABr, CHCl3, H2O, 2h, 20°C; (g) acyl chloride of proper acid (benzoyl chloride, 4-acetoxy cinnamoyl
chloride or 4-acetoxy-3-methoxy cinnamoyl chloride), pyridine, CHCl3, 24h, 20°C; (h) 36% HCl, CHCl3, EtOH (1:1:3), 24-48h,
20°C.
Further aldehyde groups of glycosides 8, 9 and 10 were reduced by sodium borohydride
using cetyltrimethylammonium bromide (CTMABr) as a phase transfer catalyst in chloroform-
water system20. The reaction proceeds at ambient temperature with almost quantitative yields.
The best results were obtained when using CTMABr in quantities of 1% mol. of the substrate21.
Sodium borohydride in water or alcohol solvents without any phase transfer catalysis condition22
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was found to be unsuited, because complete removal of acetyl groups takes place, which, as a
result, requires re-acetylation.
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Reduced glycosides 11 and 12 were subjected to acylation with benzoylchloride in pyridine
to produce desoxysalireposide tetraacetate 14 and salireposide pentaacetate 15, respectively.
Glycosides 16, 17, 18, were synthesized in the same way, applying acylation of compounds
11 and 12 with the acyl chloride of convenient acid23.
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Selective cleavage of acetyl groups in the presence of benzoyl is possible if the H2SO4-
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acetone24 system is applied, but cleavage of benzoyl group is still significant. The best results
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were obtained by using HBF4 - MeOH25 and HC1 - MeOH26,
systems. However, the
application of these systems is limited for compounds containing acid-labile acyl groups instead
of benzoyl one. Thus, for selective removal of acetyl groups in presence of benzoyl we applied
the following system: HCl (aqueous solution,  = 1.18 g/mL)-EtOH (96%)-chloroform in a
molar ratio of HCl-glycoside 54:1 and the concentration of HCl in ethanol-chloroform mixture
(volume ratio 3:1) 2.4 mol/L at the ambient temperature for 48 h.
The reaction at the ambient temperature resulted in a successful cleavage of protective acetyl
groups not only for glycoside 13,14 and 15, containing benzoyl group, but also for 16, 17 and 18,
containing 4-acetoxy cinnamoyl and 4-acetoxy-3-methoxy cinnamoyl groups, respectively,
without significant cleavage of these groups and without breaking the glycosidic bond. Yet, it
was observed that benzoyl group has a high resistance to hydrolysis under these conditions, as
compared to 4-acetoxy cinnamoyl and 4-acetoxy-3-methoxy cinnamoyl groups. Also, when
monitoring the reaction by HPLC, ethyl esters of 4-acetoxy-3-methoxy cinnamic and 4-acetoxy
cinnamic acids were detected. The formation of benzoic acid or ethylbenzoate in the case of
substances 13, 14 and 15 was not significant.
It was established that glycosides anomerization and configuration change did not occur
under the described conditions. Chemical shifts of anomeric carbon atoms for both glycosides
(101.4-104.1 ppm, depending on the solvent), and their per-acetates (97.0-99.8 ppm) in 13C
NMR spectrum correspond to chemical shifts of anomeric carbon atoms for glycosides of β-
configuration28. Phenolglycosides 1-4 are identical with naturally-ocuring glycosides according
to published data29,7. Also compound 1 was isolated from Populus tremula bark using method
described in literature7, and physicochemical characteristics of natural and synthetic samples
were identical.
We found out that the selective deacetylation reaction does not cause acyl groups migration,
as it corresponds to the base conditions33. To prove this, synthetic glycosides were re-acetylated
to yield compounds with physicochemical characteristics identical to original acetates30,32,34
.
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In conclusion, we have developed a simple synthetic pathway for some natural
phenolglycosides derivatives of salicyl and gentisyl alcohols involving simple and readily
accessible starting materials such as glucose and hydroquinone or salicylic aldehyde. The
developed scheme allows obtaining glycosides of β-configuration regioselectively. Also
investigation of these latter issues are currently in progress.
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3. Experimental
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3.1 General Experimental Procedures.
Melting points, which are uncorrected, were determined using a Kofler hot stage apparatus.
UV spectroscopic data were obtained with SF-102 spectrophotometer. IR spectra were recorded
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with IR Fourier spectrophotometer Spectrum BX II using KBr disks. The H and C NMR
spectra were recorded on Bruker-300 MMX spectrometer at 300 and 75.5 MHz, respectively, in
CDCl3, DMSO-d6 and МеOD-d4 with TMS as an internal standard and Cr(acac)3 as a relaxant.
The chemical shifts are given in δ (ppm) and the spin−spin coupling constants (J) in hertz. GC-
MS analysis was performed using Aligent 7890A/5975C GC/MSD instrument, electron energy
70 eV. The ion source temperature was 230°C, with the quadrupole temperature 150°C and
evaporator temperature 315°С, employing a 30.000×0.25 mm×0.25 μm HP - 5MS fused-silica
capillary column. Helium was used as carrier gas at a constant flow of 1 mL/min and an inlet
temperature of 315oC. The column temperature mode: 2 min at 150°C, 150-315°С (20°С/min),
and 25 min at 315оС. TLC were performed using plates Silufol-UV 254 and Sorbfil-UV 254
using benzene-ethanol 9:1 (method A) or chloroform-methanol 4:1 (B) mixtures as eluents.
HPLC analysis was carried out with the liquid chromatographer Agilent Compact LC with
column 150×4.6 Exlips Plus C-18 (5 μm). Analysis was performed using 0.1% trifluoroacetic
acid in H2O-CH3CN as mobile phase, at gradient elution (from 0% to 100 % CH3CN in 20 min)
at a flow rate of 1 mL/min. Probe volume was 20 μL. UV detection was performed at 220 nm.
Accurate mass measurement was performed on an Agilent 1200 series LC system coupled with
an Agilent 6210 TOF mass spectrometer. Silica gel MN Kieselgel 60 0.04-0.063 mm was used
for column chromatography. Commercially available solvents were used after drying with CaCl2.
3.2. 2-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyloxy) bromide (ABG) was obtained
according to the method described, lit.3 and additionally recrystallized from Et2O. Yield 58%,
mp 88 оC.
3.3. Monoacetylhydroquinone (7а) was obtained according to the method17 by acetylation
of hydroquinone with acetic anhydride. Yield 56%; mp 49-50 оC; 1H NMR (CDCl3, 300 MHz) δ:
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2.28 (3Н, s, COCH3); 6.67 (2Н, d, J=7.8, Hz, H-2, H-6); 6.86 (2Н, d, J=8.1, Hz, H-3, H-6). C
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NMR (CDCl3, 75.5 MHz) δ: 21.1 (CH3, СОСН3); 116.4 (С-2,С-6); 122.3 (С-3, С-5); 143.7 (С-
4); 153.7 (С-1); 171.2 (C, СОСН3). MS m/z 152 [M]+ (19), 110 (100), 43 (55).
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3.4. Monobenzoylhydroquinone (7b). To 11.44 g (0.104 mol) of hydroquinone dissolved in
120 ml 0.43 n. NaOH (0.052 mol) cooled to 5 °C. 6 ml (0.052 mol) benzoylchloride was drop-
added for one hour while agitating the solution at 5°C. The mixture was stirred at this
temperature for 40 min. The precipitate was filtered, washed with saturated solution of NaHCO3
and water. Recrystallization from toluene gave light brown crystals, yield 4.34 g (39%); mp 162-
163 °C, lit.34 163°C. 1H NMR (CDCl3, 300 MHz) δ: 6.80 (2Н, d, H-6, J=8.7, Hz, H-2); 7.03 (2Н,
d, J=8.7, Hz, H-3, H-5); 7.51 (2Н, m, H-10, H-12); 7.64 (1Н, m, H-11); 8.19 (2Н, d, J=8.1, Hz,
H-9, H-13). 13C NMR (CDCl3, 75.5 MHz) δ: 116.8 (C-2, С-6); 122.7 (С-5, С-3); 128.7 (С-10, С-
12); 130.3 (С-8, С-9,С-13); 133.80 (С-11); 144.2 (С-4); 153.9 (С-1); 165.9 (С-7).
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3.5. 2-hydroxy-5-acyloxy benzaldehyde (6a, 6b). General method. To 0.01 mol of
monoacylhydroqinone (7a or 7b), dissolved in 20 mL trifluoroacetic acid, 0.04 mol of
hexamethylenetetramine was added, and the mixture was stirred at temperature 80°C for 1 h. The
reaction mixture was diluted with 60 mL 0.35 % HCl and extracted with CHCl3 (3×30 mL). The
extracts were combined, washed with saturated NaСl, water, dried over Na2SO4, subjected to
flash column chromatography, and evaporated.
3.5.1. 2-hydroxy-5-acetyloxy benzaldehyde (6a). Recrystallization from water gave (6a) as
white needles (37%): mp 78-79 °C. IR (KBr, νmax/cm–1): 3075 (OH); 1766 (С=О); 1674 (HC=O)
1587 (Ar);1488 (Ar); 1373 (C-H); 1224 (C-O-C); 1142, 1015(C-O); 913 (C-H); 834 (Ar), 710
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(Ar). H NMR (CDCl3, 300 MHz) δ: 2.30 (3Н, s, COCH3); 6.97 (1Н, d, J=8.7, Hz, Н-6,); 7.22
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(1Н, dd, J=2.7, 9.0, Hz, Н-5,); 7.31 (1Н, d, J=2.7, Hz, Н-3); 9.83 (1Н, s, СHО). C NMR
(CDCl3, 75.5 MHz) δ: 20.9 (CH3, COCH3); 118.7(С-2); 120.1(С-6); 125.4(С-3); 130.66(С-
5); 142.93(С-4); 159.18(С-1); 169.46(C, СOCH3); 195.80(СHO). MS m/z 180 [M]+ 180 (10),
138 (100), 120 (7), 92 (8), 43 (19).
3.5.2. 2-hydroxy-5-benzoyloxy benzaldehyde (6b). Recrystallization from water gave
(6b) as white needles (27%): mp 109-110 °С. IR (KBr, νmax/cm–1): 3063 (OH); 2863 (СН); 1734
(СО); 1665 (HC=O) 1627, 1587 (Ar);1479, 1451 (Ar); 1371 (C-H); 1231 (C-O-C); 1061(C-O);
911 (CH); 714 (Ar). 1H NMR (CDCl3, 300 MHz) δ: 7.04 (1Н, d, J=8.7, Hz, H-6); 7.37 (1Н, dd,
J=8.7, 2.4, Hz, H-5); 7.46 (1Н, d, J=2.4, Hz, H-3); 7.50 (2Н, m, H-10, H-12); 7.64, (1Н, m, H-
11); 8.18, (2Н, m, H-9, H-13); 9.88 (1H, s, СОН). 13C NMR (CDCl3, 75.5 MHz) δ: 118.8 (С-2);
120.3 (С-6); 125.6 (С-3); 128.7 (С-10,С-12); 129.0 (С-5); 130.2 (C-9,С-13); 130.9 (С-8); 133.9
(С-11); 143.3 (С-4); 159.4 (С-1); 165.3 (С7); 195.8 (СHO). MS m/z 242 [M]+ (5), 105 (100), 77
(35).
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3.6.
2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-
benzaldehyde
(helicin
tetraacetate) (8) was obtained from (5) according to the method described18. Yield 16%, mp
142-143 °C. IR (KBr, νmax/cm–1): 2964, 2777 (С-Н); 1762 (С=О), 1685 (НС=О); 1602 (Ar) 1484
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(Ar); 1378, 1367 (C-H); 1234(С-О) 1071, 1041(C-O); 909 (C-H); 764 (Ar). H NMR (DMSO-
d6, 300 MHz) δ: 1.99, 2.01, 2.02 (4×3Н, s, COCH3); 4.09 (1Н, m, Н-5'); 4.20-4.32 (2Н, m, H-6'a,
H-6'b); 5.02 (1Н, m, H-4'); 5.16 (1Н, m, Hz, Н-3'); 5.43 (1Н, t, J=9.3, Hz, Н-2'); 5.70 (1Н, d,
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J=7.8, Hz, Н-1',); 7.20 (2Н, m, Н-4, H-6); 7.72 (2Н, m, Н-3, H-5); 10.15 (1Н, s, СНО). C
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NMR (DMSO-d6, 75.5 MHz) δ: 20.3 (4×COCH3); 61.5 (С-6'); 67.9 (С-4'); 70.5 (C-2'); 70.9 (С-
5'); 71.5(С-3'); 97.2(С-1'); 115.9(С-6); 123.1(С-4); 124.9(С-2); 127.5(С-3); 136.3(С-5);
158.3(С-1); 169.3, 169.5, 169.9(4× COCH3); 189.1(СHО).
3.7. 2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-5-acyloxy benzaldehyde (9,10).
General method. To a mixture of 7 mmol compound 6a or 6b and 7 mmol ABG in 3 mL
quinoline was added 7 mmol Ag2O, and the mixture was stirred until thickening and kept for 1 h
under room temperature. The reaction mixture was diluted with 20 mL CHCl3, centrifuged (10
min, 1500 rpm), CHCl3 was separated, washed with 0.1 M H2SO4 (3×5 mL), water, dried over
Na2SO4, subjected to flash column chromatography, and evaporated.
3.7.1. 2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-5-acetyloxy benzaldehyde (9).
Recrystallization from ethanol gave (9) as white needles (25%), mp 144-146 °C. IR (KBr,
νmax/cm–1): 3484 (С-Н); 2948, 2903 (СН3); 1760, 1690 (С=О); 1607 (Ar) 1489 (Ar); 1379 (C-
H); 1236 (C-O); 1072, 1041 (C-O); 908 (C-H). 1H NMR (CDCl3, 300 MHz) δ: 2.03, 2.04, 2.05,
2.06 (4×3Н, s, COCH3); 2.29 (3Н, s, COCH3); 3.85 (1Н, m, H-5'); 4.14-4.31 (2Н, m, H-6'a, H-
6'b); 5.13-5.38 (4Н, m, Н-1', H-2', H-3', H-4'); 7.12 (1Н, d, J=9.0, Hz, H-6); 7.26 (1Н, dd, J=3.0,
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9.0, Hz, H-5); 7.54 (1Н, d, J=2.7, Hz, H-3); 10.29 (1Н, s, СНО). C NMR (CDCl3, 75.5 MHz)
δ: 20.5 (CH3, COCH3); 20.9 (4×СH3, COCH3); 61.7 (С-6'); 68.0 (С4'); 70.8 (С-2'); 72.3(С-3', С-
5'); 99.4(С-1'); 117.5(С-6); 120.9(С-3); 127.0(С-2); 128.8(С-5); 146.3(С-4); 156.2(С-1); 169.3;
170.1; 170.4(5×C, COCH3); 188.2(СHO). HRESIMS Calcd for C23H26O13 533,12656 [M+Na]+.
Found 533,12428 [M+Na]+.
3.7.2. 2-(2,3,4,6-tetra-О-acetyl-β-D-glucopyranosyloxy)-5-benzoyloxy benzaldehyde
(10). Recrystallization from ethanol gave (10) as white needles (47%), mp 124-125 °C. IR (KBr,
νmax/cm–1): 3484 (С-Н); 3074, 2887 (СН3); 1749, 1687 (С=О); 1611 (Ar) 1490 (Ar); 1379 (C-
1
H); 1221 (C-O); 1063, 1036 (C-O); 906 (C-H); 707 (Ar). H NMR (CDCl3, 300 MHz) δ: 2.04,
2.05, 2.07 (4×3Н, s, COCH3); 3.88 (1Н, m, H-5'); 4.15 (2Н, m, H-6'a, H-6'b); 5.17-5.41 (4Н, m,
Н-1', H-2', H-3', H-4'); 7.18 (1Н, d, J=9.3, Hz, Н-6); 7.40 (1Н, dd, J=3.0, 9.0, Hz, Н-5); 7.48
(2Н, m, Н-10, H-12); 7.62 (1Н, d, J=7.5, Hz, Н-11); 7.67 (1Н, d, J=2.7, Hz, Н-3); 8.16 (2Н, d,
J=7.8, Hz, Н-9, Н-13); 10.30 (1Н, s, СНО). 13C NMR (CDCl3, 75.5 MHz) δ: 20.5 (СH3,
7

COCH3); 61.7 (С-6'); 68.0 (С-4'); 70.8 (С-2'); 72.3(С-3', С-5'); 99.4(С-1'); 117.6 (С-6); 121.0
(С-3); 122.6 (C-5); 127.1(С-2); 128.6(C-10, С-12); 128.8(C-8); 129.0 (C-9); 130.13(C-13);
133.9(C-11); 146.6(С-4); 156.2 (C-1); 165.0(C-7); 169.1; 169.3; 170.0; 170.4(4×C, COCH3);
188.0(CHO). HRESIMS Calcd for C28H28O13 595,14221 [M+Na]+. Found 595,14412 [M+Na]+.
3.8. 2-(2,3,4,6-tetra-О-acetyl-β-D-glucopyranosyloxy) benzyl alcohol (11, 12, 13).
General method. To 0.7 mmol of correspond glycoside (8 - 10) dissolved in 5 mL CHCl3, was
added a solution of NaBH4 (0.7 mmol) in 2 mL water and 0.0025 g (1% mol) CTMABr. The
reaction mixture was stirred at room temperature until TLC showed complete conversion of
starting material (2 h). CHCl3 was separated, washed with 0.1 M HCl (3×5 mL), water, dried
over Na2SO4, evaporated, and recrystallized from ethanol.
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3.8.1. 2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)- benzyl alcohol (salicine
tetraacetate) (11) Yield 95%, mp 117-119 °C. IR (KBr, νmax/cm–1): 3479 (ОН); 2970 (СН3);
1754 (С=О); 1610 (Ar) 1490 (Ar); 1385,1365 (C-H); 1240 (C-O); 1068, 1037 (C-O); 910 (C-H);
759 (Ar). 1H NMR (DMSO-d6, 300 MHz) δ: 1.98, 2.02, 2.02, 2.04 (4×3Н, s, COCH3); 4.07 (1Н,
d, J=9.9, Hz, Н-5'); 4.21 (1H, m, H-6'b); 4.39 (1Н, m, H-6'a); 4.24 (1H, m, H-7b), 4.39 (1Н, m,
H-7a); 4.97 (1Н, m, H-4'); 5.06 (1Н, m, Н-3'); 5.39-5.47 (2Н, m, Н-2', Н-1'); 7.03 (2Н, m, Н-6,
H-4); 7. 21 (1Н, m, Н-5); 7.41 (1Н, d, J=6.9, Hz, Н-3). 13C NMR (DMSO-d6, 75.5 MHz) δ: 20.4
(4×СH3, COCH3); 57.3 (С-7); 61.6 (C-6'); 68.1 (С-4'); 70.5 (С-2'); 70.7 (С-5'); 71.7(С-3');
97.5(С-1'); 114.3(С-6); 122.6(С-4); 127.1(С-3); 127.5(С-5); 131.4(С-2); 153.1(С-1); 169.1;
169.3, 169.5 169.6 (4×С, COCH3).
3.8.2. 2-(2,3,4,6-tetra-О-acetyl-β-D-glucopyranozyloxy)- 5- acetyloxy benzyl alcohol
(12) Yield 93%, mp 110-111 °C. IR (KBr, νmax/cm–1): 3547 (OH); 2982 (С-Н); 1758 (С=О);
1507, 1490 (Ar); 1374 (C-H); 1227, 1194 (C-O-C); 1065, 1043(C-O); 911 (C-H); 826, 706 (Ar).
1H NMR (DMSO-d6, 300 MHz) δ: 1.98, 2.01, 2.02, 2.05 (4×3Н, s, COCH3); 2.25 (3Н, s,
COCH3); 4.08 (1Н, d, J=9.9, Hz, Н-5'); 4.21, (1H, m, H-6'b); 4.23 (1H, m, H-7b); 4.38 (2Н, m,
H-6'a, H-7a); 4.98 (1Н, m, H-4',); 5.06 т (1Н, t, J=9.0, Hz,Н-3'); 5.39-5.46 (2Н, m, Н-2', Н-1');
13
6.97 (1Н, d, J=8.4, Hz, Н-5); 7. 05 д (1Н, d, J=8.7, Hz, Н-6); 7.14 (1Н, s, Н-3). C NMR
(DMSO-d6, 75.5 MHz) δ: 20.4 (4×СH3, COCH3); 20.7 (СH3, COCH3); 57.1 (С-7); 61.6 (C-6');
68.1 (С-4'); 70.5 (С-2'); 70.8 (С-5'); 71.7(С-3'); 97.8(С-1'); 115.3(С-6); 120.2(С-5); 120.4(С-3);
133.0(С-2); 145.7(С-4); 150.4(C-1); 169.1; 169.3, 169.4, 169.5, 169.9(5×С, COCH3). HRESIMS
Calcd for C23H28O13 535,14221 [M+Na]+. Found 535,16732 [M+Na]+.
3.8.3. 2-(2,3,4,6-tetra-О-acetyl-β-D-glucopyranozyloxy)- 5- benzoyloxy benzyl alcohol
(iso-salireposide tetraacetate) (13). Yield 65%, mp 84-86 °C. IR (KBr, νmax/cm–1): 3526 (OH);
2925 (С-Н); 1750 (С=О); 1507, 1497 (Ar); 1375 (C-H); 1227 (C-O-C); 1067(C-O); 908 (C-H);
803, 706 (Ar). 1H NMR (CDCl3, 300 MHz) δ: 2.05, 2.07, 2.11 (4×3Н, s, COCH3); 3.85 (1Н, m,
8

Н-5'); 4.15-4.31 (2Н, m, H-6'a, H-6'b); 4.51 (1Н, d, J=13.5, Hz, H-7b); 4.67 (1Н, d, J=13.2, Hz,
H-7a); 5.09-5.33 (4Н, m, Н-1', H-2', H-3', H-4'); 7.05 (2Н, m, Н-5, H-6); 7.23 (1Н, m, Н-3); 7.48
(2Н, m, Н-10, Н-12); 7.61 (1Н, m, Н-11); 8.17 (2Н, d, J=7.2, Hz, Н-9, Н-13). 13C NMR (CDCl3,
75.5 MHz) δ: 20.3 (4×СH3, COCH3); 60.3 (C-7); 61.5 (C-6'); 67.9 (C-4'); 70.8 (С-2'); 71.8 (C-
5'); 72.1(C-3'); 99.7 (C-1'); 116.5(С-6); 121.5(С-3); 122.2(С-5); 128.4(С-11, С-13); 129.0(С-9);
129.9 (С-10,С-14); 132.8 (С-2); 133.5(C-12); 146.4(C-4); 151.7(C-1); 165.0(C, C=O); 169.1;
169.3; 169.9; 170.3(4×C, COCH3). HRESIMS Calcd for C28H30O13 597,15786 [M+Na]+. Found
597,16006 [M+Na]+.
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3.9. Acylation of glycosides (11, 12). General method. To a solution of glycoside (11 or
12) (0.2 mmol) in 1 mL CHCl3, was added chloroanhydride of correspond acid (benzoylchloride,
4-acetyloxycynnamic acid chloroanhydride or 3-methoxy-4-acetyloxycynnamic acid
chloroanhydride) (0.22 mmol) and 0.26 mmol of pyridine. The reaction mixture was kept at
room temperature for 24 h and diluted with 20 mL CHCl3. The solution was washed 0.1 M
H2SO4, sat. Na2CO3, water, dried over Na2SO4 and evaporated. The residue was recrystallized
from ethanol.
3.9.1.
2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-benzylbenzoate
(desoxysalireposide tetraacetate) (14) Was obtained from glycoside (11) and benzoylchloride.
Yield 50%, mp 82-83°C. IR (KBr, νmax/cm–1): 3071, 2960 (С-Н); 1753 (С=О); 1507, 1457 (Ar);
1377 (C-H); 1235 (C-O-C); 1070, 1046(C-O); 908 (C-H); 761 (Ar). 1H NMR (CDCl3, 300 MHz)
δ: 2.03, 2.04, 2.05, 2.08 (4×3Н, s, COCH3, at 2', 3', 4', and 6'); 3.86 (1Н, m, Н-5'); 4.15-4.32 (2Н,
m, H-6'b, H-6'a); 5.10-5.45 (4Н, m, Н1', H-2', H-3', H-4'); 5.30 (2Н, m, Н-7a, H-7b); 7.09 (2Н,
m, Н-4, H-6); 7.27 (1Н, m, Н-5); 7.42 (3Н, m, Н-3, H-11, H-13); 7.54 (1Н, m, Н-12); 8.06 (2Н,
13
dd, J=1.5, 8.4, Hz, Н-10, H-14). C NMR (CDCl3, 75.5 MHz) δ: 20.6(4×СH3, COCH3); 61.3
(С-7); 61.8 (С-6'); 68.2(С-4'); 70.9(С-2'); 72.0(С-5'); 72.6(С-3'); 99.4(С-1'); 115.9(С-6);
123.6(С-4); 126.4(С-2); 128.4(С-11, С-13); 129.3(С-3); 129.6(С-5, С-10, С-14); 130.0(С-9);
133.1 (C-12);154.4(С-1); 166.2(C-8); 169.3, 170.2, 170.5(4×C, COCH3). HRESIMS Calcd for
C28H30O12 581,16295 [M+Na]+. Found 581,19996 [M+Na]+.
3.9.2. 2-(2,3,4,6-tetra-О-acetyl-β-D-glucopyranosyloxy)- 5- acetyloxy benzylbenzoate
(salireposide pentaacetate) (15) Was obtained from glycoside (12) and benzoylchloride. Yield
45%, mp 127-128 °C. UV λmax (EtOH)/nm: 225, 274. IR (KBr, νmax/cm–1): 2940 (С-Н); 1752
(С=О); 1603 (Ar) 1498 (Ar); 1375 (C-H); 1232 (C-O-С); 1085, 1043 (C-O); 908 (C-H); 708
1
(Ar). H NMR (CDCl3, 300 MHz) δ: 2.03, 2.05, 2.07, 2.08 (4×3Н, s, COCH3); 2.28 (3Н, s,
COCH3); 3.83 (1Н, m, H-5'); 4.15-4.31м (2Н, m, H-6'a, H-6'b); 5.04-5.41м (4Н, m, H-1', H-2',
H-3', H-4'); 5.28 (2Н, m, Н-7a, H-7b); 7.00 (1Н, dd, J=3.0, 9.0, Hz, Н-5); 7.11 (1Н, d, J=8.7, Hz,
Н-6); 7.16 (1Н, d, J=2.7, Hz, Н-3); 7.43 (2Н, m, Н-11, H-13); 7.55 (1Н, m, Н-12); 8.06 (2Н, d,
9

13
J=7.2, Hz, H-10, H-14). C NMR (CDCl3, 75.5 MHz) δ: 20.6 (4×CH3, COCH3); 21.1 (CH3,
COCH3); 60.9 (С-7); 61.8 (С-6'); 68.2(С-4'); 70.9(С-2'); 72.0(С-5'); 72.5(С-3'); 99.8(C-1');
117.2(С-6); 122.0(С-5); 122.1(С-3); 128.0(С-2); 128.4(С-11, С-13); 129.7(С-9, С-10, С-14);
133.1(С-12); 146.3(С-4); 151.8(С-1); 166.1(С-8); 169.3, 169.6, 170.2, 170.5(5×C,COCH3).
3.9.3. 2-(2,3,4,6-tetra-О-acetyl-β-D-glucopyranosyloxy)- 5- acetyloxy benzyl (4-
acetoxy) cinnamoate (populoside A hexaacetate) (16) Was obtained from glycoside (12) and
4-acetyloxycynnamoyl chloride. Yield 42%, mp 113-114 °C. UV λmax (EtOH)/nm: 218, 283. IR
(KBr, νmax/cm–1): 2940 (С-Н); 1752(С=О); 1640, 1603 (Ar) 1508 (Ar); 1373 (C-H); 1222 (C-O-
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С); 1037 (C-O); 907 (C-H); 838 (Ar). H NMR (CDCl3, 300 MHz) δ: 2.03, 2.04, 2.07, 2.11
(4×3Н, s, COCH3); 2,28 (3Н, s, COCH3); 2.30 (3Н, s, COCH3); 3.84 (1Н, m, Н-5'); 4.16-4.30
(2Н, m, Н-6'a, H-6'b); 5.03-5.31 (4Н, m, H-1', H-2', H-3', H-4'); 5.29 (2Н, m, Н-7a, H-7b); 6.40
(1Н, d, J=16.2, Hz, Н-9,); 6.98 (1Н, dd, J=2.7, 8.7, Hz, Н-5); 7.10 (4H, m, Н-3, Н-6, H-13,H-
13
15); 7.53 (2H, d, J=8.7, Hz, Н-12, H-16); 7.67 (1H, d, J=15.9, Hz, Н-10). C NMR (CDCl3,
75.5 MHz) δ: 20. 6 (4×СH3, COCH3); 21.1(2×СH3, COCH3); 60.5(С-7); 61.8(С-6'); 68.2(С-4');
70.9(С-2'); 72.0(С-5'); 72.6(С-3'); 99.8(С-1'); 117.2 (С-9); 117.7(С-6); 122.1(С-3, С-5, С-13, С-
15); 127.9(С-2); 129.3(С-12, С-16); 132.0(С-11); 144.2(С-4, С-10); 146.3(C-1); 151.9(С-14);
166.3(С-8); 169.1, 169.3, 169.6, 170.2, 170.5(6×C, COCH3). HRESIMS Calcd for C34H36O16
723,18956 [M+Na]+. Found 723,18345 [M+Na]+.
3.9.4.
2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-
benzyl
(4-acetoxy)
cinnamoate (populoside B pentaacetate) (17) Was obtained from glycoside (11) and 4-
acetyloxycynnamoyl chloride. Yield 30%, mp 123-124 °C. UV λmax (EtOH)/nm: 283. IR (KBr,
νmax/cm–1): 2963 (С-Н); 1748, 1714 (С=О); 1641, 1603 (Ar) 1509, 1495 (Ar); 1373 (C-H); 1230
1
(C-O); 1068, 1036 (C-O); 910 (C-H); 763(Ar). H NMR (CDCl3, 300 MHz) δ: 2.04, 2.04, 2.07,
2.10 (4×3Н, s, COCH3); 2,31 (3Н, s, COCH3); 3.88 (1Н, m, Н-5'); 4.17-4.32 (2Н, m, Н-6'a, H-
6'b); 5.09-5.32 (4Н, m, H-1', H-2', H-3', H-4'); 5.27 (2Н, m, Н-7a, H-7b); 6.41 (1Н, d, J=15.9,
Hz, Н-9); 7.08 (4Н, m, Н-4, H-6, H-13, H-15); 7.29 (1Н, m, Н-3); 7.39 (1H, d, J=7.2, Hz, H-5);
13
7.53 (2H, d, J=8.4, Hz, Н-12, H-16); 7.67 (1H, d, J=15.9, Hz, Н-10). C NMR (CDCl3, 75.5
MHz) δ: 20.6 (4×СH3, COCH3); 21.1(CH3, COCH3); 61.0(С-7); 61.9(С-6'); 68.3(С-4'); 71.0(С-
2'); 72.0(С-5'); 72.6(С-3'); 99.4(С-1'); 115.9(С-6); 118.0(С-9); 122.1(С-13, С-15); 123.6(С-4);
126.3(С-2); 129.2(С-5); 129.4(C-3); 129.5(С-12, С-16); 132.1(С-11); 144.0(C-10); 152.1(С-1);
154.5(С-14); 166.5(C-8); 169.1, 169.4, 170.2, 170.5(5×C, COCH3). HRESIMS Calcd for
C32H34O14 665,18408 [M+Na]+. Found 665,17862 [M+Na]+.
3.9.5. 2-(2,3,4,6-tetra-О-acetyl-β-D-glucopyranosyloxy)- benzyl (4-acetoxy-3-methoxy)
cinnamoate (populoside С pentaacetate) (18) Was obtained from glycoside (11) and 3-
methoxy-4-acetyloxycynnamoyl chloride. Yield 55%, mp 91-92 °C. UV λmax (EtOH)/nm: 281.
10

IR (KBr, νmax/cm–1): 3019, 2941 (С-Н); 1762, 1718 (С=О); 1643, 1602 (Ar) 15.15, 1496 (Ar);
1373 (C-H); 1284, 1228 (C-O-С); 1036 (C-O); 908 (C-H); 760(Ar). 1H NMR (CDCl3, 300 MHz)
δ: 2.03, 2.04, 2.06, 2.09 (4×3Н, s, COCH3); 2,31 (3Н, COCH3); 3.85 (4Н, s, OCH3; 1Н, Н-5');
4.17-4.31 (2Н, m, Н-6'a, H-6'b); 5.09-5.31 (4Н, m, H-1', H-2', H-3', H-4'); 5.27 (2Н, m, Н-7a, H-
7b); 6.40 (1Н, d, J=15.9, Hz, H-9); 7.02 (2Н, m, Н-4, H-6); 7.10 (3Н, m, Н-12, H-15, H-16);
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7.29 (2Н, m, Н-3, H-5); 7.64 (1H, d, J=15.9, Hz, Н-10). C NMR (CDCl3, 75.5 MHz) δ: 20.6
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(5×СH3, COCH3); 55.9 (OCH3); 61.1(С-7); 61.9(С-6'); 68.3(С-4'); 71.0(С-2'); 72.0(С-5');
72.6(С-3'); 99.4(С-1'); 111.3 (С-12); 115.9(С-6); 118.1(С-9); 121.3(С-16); 123.3(С-4); 123.6
(С-15); 126.3 (С-2,); 129.5(С-5); 129.6(С-3); 133.3(C-11); 141.5 (С-14); 144.4(С-10); 151.4(С-
1); 154.6(С-13); 166.4(С-8); 168.7, 169.4, 170.2, 170.5(5×С, COCH3). HRESIMS Calcd for
C33H36O15 695,19464 [M+Na]+. Found 695,19193 [M+Na]+.
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3.10. Selective acetyl group cleavage. General method. To a glycoside (14, 15, 17-19)
(0.15 mmol) in a mixture of 96%-ethanol and CHCl3 in proportion 1.5 mL – 0.5 mL was added
0.5 mL 36% HCl. The reaction mixture was stirred and then kept at room temperature for a 24-
48 h. The reaction mixture was neutralized with 20%-solution of Na2CO3 until pH=7, evaporated
to dryness and product was isolated employing column chromatography by gradient elution
using chloroform and chloroform-ethanol mixture (from ratio 9:1 to 4:1). Analytical samples
were purified by recrystallization from ethanol.
3.10.1. Desoxysalireposide (19) Yield 85% mp 149-150 °C. IR (KBr, νmax/cm–1): 3361
(ОН); 2930, 2890 (С-Н); 1716 (С=О); 1635, 1604 (Ar) 1495, 1457 (Ar); 1381 (C-H); 1282,
1247 (C-O); 1094, 1046 (C-O); 712 (C-O-C). 1H NMR (DMSO-d6, 300 MHz) δ: 3.18-3.45 (4Н,
m, Н-2', H-3', H-4', Н-5'); 3.48 (1H, m, H-6'b); 3.72 (1Н, m, H-6'a); 4.88 (1Н, m, Н-1'); 5.38
(1Н, d, J=12.9, Hz, Н-7b), 5.44 (1Н, d, J=13.2, Hz, Н-7a); 7.03 (1Н, m, H-4); 7.18 (1Н, d,
J=7.8, Hz, Н-6); 7.31 (1Н, m, Н-5); 7.39 (1Н, d, J=7.2, Hz, Н-3); 7.51 (2Н, t, J=7.2, Hz, Н-11,
13
Н-13); 7.64 (1Н, d, J=7.2, Hz, Н-12); 8.01 (2Н, d, J=7.2, Hz, Н-10, Н-14). C NMR (DMSO-
d6, 75.5 MHz) δ: 60.7 (С-7) 61.7(C-6'); 69.7(С-4'); 73.3(С-2'); 76.5(С-3'); 77.1 (С-5'); 101.0 (С-
1'); 115.1 (С-6); 121.9(С-4); 124.9(С-2); 128.8 (С-11, С-13, С-3); 129.3 (С-10, С-14); 129.4 (С-
5); 129.7 (С-9); 133.4(С-12); 155.2 (С-1); 165.7 (С-8). HRESIMS Calcd for
C20H22O8 413.12069 [M+Na]+. Found 413.12362 [M+Na]+.
1
3.10.2. iso-salireposide (20) Yeild 83%, mp 168-171°C. UV λmax (EtOH)/nm: 228, 273. H
NMR (DMSO-d6, 300 MHz) δ: 4.46 (1H, dd, J=12.6, 6.0, Hz, H-6'a); 4.64 (2H, m, H-6'a, H-7b);
4.78 (1H, d, J=8.0, Hz, H-7a); 5.06 (1H, d, J=7.5, Hz, H-4'); 5.13 (1H, m, H-3'); 5.18 (1H, t,
J=7.5, Hz, H-2');5.42 (1Н, d, J=6.0, Hz, Н-1'); 7.16 (1Н, dd, J=12.0, 1.5 Hz, Н-5); 7.14 (1Н, m,
Н-3); 7.21 (1Н, m, Н-6); 7.58 (2Н, t, J=7.5, Hz, Н-11, Н-13); 7.72 (1Н, d, J=7.5, Hz, Н-12);
8.11 (2Н, d, J=7.2, Hz, Н-10, Н-14). Not specified a signal of a proton H-5', overlapped by
11

13
signal of the solvent. C NMR (DMSO-d6, 75.5 MHz) δ: 57.8 (С-7); 60.9(C-6'); 69.9(С-4');
73.1(С-2'); 76.1(С-3'); 77.0 (С-5'); 101.7 (С-1'); 115.5 (С-6); 120.0(С-3); 120.5(С-5); 129.1 (С-
11, С-13); 129.8 (С-10, С-14); 131.8 (С-2); 133.0 (С-9); 134.1(С-12); 145.1 (С-4); 152.0 (C-1);
165.0 (С-8). HRESIMS Calcd for C20H22O9 429.12632 [M+Na]+. Found 429.12852 [M+Na]+.
3.10.3. Salireposide (1) Yield 71%, mp 206-207 °C, lit.6 206-207°С. UV λmax (H2O)/nm:
226, 284. IR (KBr, νmax/cm–1): 3370 (ОН); 2931, 2890 (С-Н); 1709 (С=О); 1602 (Ar) 1453,
1478 (Ar); 1382 (C-H); 1284 (C-O); 1214 (C-O); 1084, 1049 (C-O); 907 (C-H); 711 (C-O-C).
The infrared spectrum coincides with the infrared spectrum of salireposide isolated from P.
tremula.1H NMR (MeOD-d4, 300 MHz) δ: 3.31-3.47 (4Н, m, Н-2', H-3', H-4', Н-5'); 3.60-3.89
(2Н, m, Н-6'a, H-6'b); 5.39 (2Н, m, Н-7a, H-7b); 6.75 (1Н, d, J=7.2, Hz, H-5); 6.88 (1Н, s, Н-3);
7.11 (1Н, d, J=8.7, Hz, Н-6); 7.49 (2Н, d, J=7.8, Hz, Н-10, Н-13); 7.60 (1Н, d, J=7.5, Hz, Н-
12); 8.04 (2Н, J=7.5, Hz, Н-10, Н-14). Not specified a signal of a proton H-1', overlapped by
signal of the solvent. 13C NMR (MeOD-d4, 75.5 MHz) δ: 62.4 (С-7) 63.2(C-6'); 71.0(С-4');
74.8(С-2'); 77.8(С-3', С-5'); 103.1 (С-1'); 116.1 (С-3); 117.0(С-5); 119.1(С-6); 128.5 (С-2);
129.7(С-11, С-13); 130.5 (С-10, С-14); 131.1(С-9); 134.3(С-12); 149.7(С-1); 154.0 (С-4);
168.7(С-8). The data agree well with those given in6.
3.10.4. Populoside А (2) Yield 72%, mp 162−163 °C, lit.7 162−163 °C. UV λmax (H2O)/nm:
226, 314 nm. IR (KBr, νmax/cm–1): 3400 (ОН); 2925, 2887 (С-Н); 1678 (С=О); 1606 (С=С Ar)
1515 (Ar); 1464 (C-H); 1210 (C-O); 1079, 1043 (C-O); 979 (НС=СН); 870 (C-H); 830 (C-O-
C).1H NMR (MeOD-d4, 300 MHz) δ: 3.31-3.48 (4Н, m, Н-2', H-3', H-4', Н-5'); 3.63 (1Н, m, H-
6'b); 3.86 (1H, d, J 12.0, Hz, Н-6'a); 5.24 (1Н, d, J=12.9, Hz, Н-7b); 5.34 (1H, d, J=12.6, Hz, H-
7a); 6.36 (1Н, d, J=15.9, Hz, H-9); 6.73 (1Н, dd, J=1.5, 8.4, Hz, Н-5); 6.82 (1Н, d, J=2.7, Hz, Н-
3); 6.84 (2Н, m, Н-13, Н-15); 7.10 (1Н, d, J=8.4, Hz, Н-6); 7.46 (2Н, d, J=8.4, Hz, H-12, Н-16);
7.64 (1Н, d, J=15.9, Hz, Н-10). Not specified a signal of a proton H-1', overlapped by signal of
1
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the solvent. C NMR (MeOD-d4, 75.5 MHz) δ: 62.4(С-7, С-6'); 71.2(С-4'); 74.8(С-2'); 77.8(С-
3', С-5'); 104.1(С-1'); 115.0 (С-3, C-5; С-9); 116.9(С-13, С-15,); 119.1 (С-6); 127.1(С-11);
128.6 (С-2,); 131.3(С-12, С-16); 147.0(С-10); 149.8 (С-1); 153.6 (С-4); 161.0(С-14); 169.4 (С-
8). HRESIMS Calcd for C22H24O10 471.12617 [M+Na]+. Found 471.12447 [M+Na]+. The data
agree well with those given in7.
3.10.5. Populoside B (3) Yield 30%, mp 187−188 °С, lit.7 187−188 °С. UV λmax
(H2O)/nm: 314 nm. IR (KBr, νmax/cm–1): 3388 (ОН); 2927 (С-Н); 1686 (С=О); 1605 (Ar) 1586
(Ar); 1241 (C-O); 1078 (C-O); 833 (C-O-C). 1H NMR (MeOD-d4, 300 MHz) δ: 3.31 (4Н, m, Н-
2', H-3', H-4', Н-5'); 3.69 (1H, m, H-6'b); 3.88 (1Н, d, J=12.0, Hz, Н-6'a,); 5.28 (2Н, d, J=12.9,
Hz, Н-7a, H-7b); 6.35 (1Н, d, J=15.9, Hz, H-9); 6.84 (2Н, d, J= 8.4, Hz, Н-13, Н-15); 7.25 (1Н,
t, J=7.2, Hz, Н-4); 7.21 (1Н, m, Н-6); 7.30 (1Н, m, Н-5); 7.35 (1Н, m, Н-3); 7.46 (2Н, d, J=8.4,
12

Hz, Н-12, Н-16); 7.64 (1Н, d, J=15.9, Hz, Н-10). 13C NMR (MeOD-d4, 75.5 MHz) δ: 58.0 (С-7);
62.8 (С-6'); 71.2(С-4'); 75.0(С-2'); 77.9(С-3', С-5'); 103.9(С-1'); 114.7 (С-9); 116.5 (С-6);
117.0(С-13, С-15); 123.5 (С-4); 127.0(С-11); 130.2 (С-3); 130.5(С-5); 131.2(С-12, С-16); 147.0
(С-10); 156.9(С-1); 161.9 (С-14); 169.9(С-8). HRESIMS Calcd for C22H24O9 455.14205
[M+Na]+. Found 455.13659 [M+Na]+. The data agree well with those given in7.
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2
3
4
5
6
7
8
9
3.10.6. Populoside C(4) Yield 50%, mp 107-109 °С, lit.7 109−111 °С. UV λmax (H2O)/nm:
234, 327 nm. IR (KBr, νmax/cm–1): 3370 (ОН); 2927 (С-Н); 1688 (С=О); 1615 (Ar) 1589, 1522,
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1
1450 (Ar); 1285, 1241, 1185 (C-O); 1079 (C-O); 980 (C-O-C), 751 (Ar). H NMR (DMSO-d6,
300 MHz) δ: 3.20-3.39 (4Н, m, Н-2', H-3', H-4', Н-5'); 3.69, 3.75 (2Н, m, Н-6'a, H-6'b); 3.81
(3Н, s, OCH3); 4.86 (1Н, m, Н-1'); 5.28 (2Н, m, Н-7a, H-7b); 6.53 (1Н, d, J=15.9, Hz, H-9);
6.78 (1Н, d, J=7.5, Hz, Н-15); 7.03 (1Н, m, Н-16); 7.12 (2Н, m, Н-4, Н-6); 7.33 (3Н, m, Н-3, Н-
5, Н-12); 7.58 (1Н, d, J=15.6, Hz, Н-10). 13C NMR (DMSO-d6, 75.5 MHz) δ: 56.1 (OCH3); 60.7
(С-7, C-6'); 69.7(С-4'); 73.3(С-2'); 76.5(С-3'); 77.1(С-5'); 101.0(С-1'); 111.2 (C-12); 114.4 (С-
9); 115.0(С-6); 115.5(С-15); 121.8 (С-4); 123.3(С-16); 125.2 (С-2); 125.6(С-11); 128.7(С-3);
129.3(С-5); 145.3 (С-10); 147.9(С-14); 149.4(С-13); 155.2(C-1); 166.6(С-8). HRESIMS Calcd
for C23H26O10 485.14182 [M+Na]+. Found 485.13927 [M+Na]+. The data agree well with those
given in7.
13

Acknowledgements
We would like to thank Head of the Laboratory of Petrochemical Synthesis, NIOST LLC
(Tomsk), Kolesnik Vasiliy Dmitrievich and operator Zamanova Margarita Karimovna for
assistance in obtaining spectral data of certain compounds.
Supporting Information
1H and 13C NMR spectra of compounds 1-4, 6a, 6b, 8-19, IR spectra of Salireposide (1)
isolated from P. tremula bark and obtained by synthetic means and UV spectra of selected
compounds.
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15

Graphical Abstract

Highlights
Total synthesis of natural phenolglycosides from available substrates is reported.
Synthetic phenolglycosides are proved to be identical to natural phenolglycosides.
We report acid-catalyzed acetyl groups cleavage without breaking the glycosidic bond.