Phosphorylated Glycoconjugates Based on Isosteviol, d-Arabinofuranose, and d-Ribofuranose

Article abstract of DOI:10.1134/S1070428019040158

First phosphorylated glycoconjugates were synthesized in three stages on the basis of isosteviol, d-arabinofuranose, and d-ribofuranose. In the first stage, isosteviol reacted with methyl 5-O-(p-tosyl)-2,3-di-O-benzoyl-d-ribofuranoside and methyl 5-O-(p-tosyl)-2,3-di-O-benzoyl-d-arabinofuranoside to give glycoconjugates in which the diterpenoid fragment is linked through ester bond to the carbohydrate C⁵ atom. In the second stage, the anomeric methoxy group in the furanoside fragment was replaced by bromine, and the resulting 2,3-di-O-benzoyl-d-ribofuranosyl and 2,3-di-O-benzoyl-d-arabinofuranosyl bromides were treated with dibutyl phosphate to afford the target phosphorylated derivatives.

Full text of DOI:10.1134/S1070428019040158

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2019, Vol. 55, No. 4, pp. 508–513. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 4, pp. 608–614.
Phosphorylated Glycoconjugates Based on Isosteviol,
D-Arabinofuranose, and D-Ribofuranose
R. R. Sharipovaa, M. G. Belenoka, I. Yu. Strobykinaa, and V. E. Kataeva*
a Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
ul. Akademika Arbuzova 8, Kazan, 420029 Tatarstan, Russia
*e-mail: kataev@iopc.ru
Received April 5, 2018; revised February 10, 2019; accepted February 19, 2019
Abstract—First phosphorylated glycoconjugates were synthesized in three stages on the basis of isosteviol,
D-arabinofuranose, and D-ribofuranose. In the first stage, isosteviol reacted with methyl 5-O-(p-tosyl)-2,3-di-
O-benzoyl-D-ribofuranoside and methyl 5-O-(p-tosyl)-2,3-di-O-benzoyl-D-arabinofuranoside to give glycocon-
jugates in which the diterpenoid fragment is linked through ester bond to the carbohydrate C5 atom. In the
second stage, the anomeric methoxy group in the furanoside fragment was replaced by bromine, and the
resulting 2,3-di-O-benzoyl-D-ribofuranosyl and 2,3-di-O-benzoyl-D-arabinofuranosyl bromides were treated
with dibutyl phosphate to afford the target phosphorylated derivatives.
Keywords: isosteviol, arabinofuranose, ribose, glycoterpenoids, glycoconjugates, glycosides.
DOI: 10.1134/S1070428019040158
Secondary metabolites isolated from various natural
sources are widely used as starting compounds for the
design of new therapeutic agents. An example is
diterpenoid isosteviol 9 (16-oxo-ent-beyeran-19-oic
acid) which is obtained by acid hydrolysis of glyco-
sides from Stevia rebaudiana [1]; glycoside extract
from that plant is sold as a low-calorie sweetener under
different trade names in distribution networks. Like all
natural terpenoids, isosteviol is a biologically active
compound exhibiting moderate antihyperglycemic
[2, 3], cardioprotective [4], anticancer [2, 5], antituber-
cular [6], anti-inflammatory [2], antibacterial, and
antifungal activities [7]. Chemical modification of iso-
steviol not only enhanced its antitubercular [6, 8–10],
anticancer [12, 13], and antibacterial activities [14] but
also endowed it with antiviral and [15] and antimitotic
properties [16].
In continuation of our works on the synthesis and
biological activity of isosteviol [17], betulin [18, 19],
and allobetulin glycoconjugates [20] with various
monosaccharides, herein we describe the first synthesis
of phosphorylated isosteviol glycoconjugates with
D-arabinofuranose and D-ribofuranose.
In the first stage, D-arabinopiranose 1 was con-
verted to methyl 5-O-p-tosyl-α/β-D-arabinofuranoside
3 according to the procedure described in [21], and
benzoylation of 3 gave methyl 5-O-p-tosyl-2,3-di-O-
benzoyl-α-D-arabinofuranoside 4 (Scheme 1). Like-
wise, from D-ribose 5 we obtained methyl 5-O-p-tosyl-
2,3-di-O-benzoyl-β-D-ribofuranoside 8.
In the second stage, glycosides 4 and 8 were con-
jugated to isosteviol 9 via reaction in acetonitrile in the
presence of potassium carbonate under argon. Glyco-
conjugates 10 and 12 thus formed were isolated in 43
and 21% yield, respectively, by silica gel column
chromatography (Scheme 2). The formation of 10 and
12 was confirmed by their MALDI mass spectra which
showed ion peaks with m/z 695.29 [M + Na]+
(C40H48NaO9, M 695.32) (10) and m/z 695.42
[M + Na]+ (C40H48NaO9, M 695.32), 711.41 [M + K]+
(C40H48KO9, M 711.29) (12). Glycoconjugate 10 was
isolated as a single α-anomer. This followed from the
1H and 13C NMR spectra which contained only one set
of signals; the anomeric proton resonated in the
1H NMR spectrum as a singlet at δ 5.11 ppm (cf. [22]).
Compound 12 was pure β-anomer, and its anomeric
proton resonated as a singlet at δ 5.14 ppm (cf. [23]).
The methoxy group in 10 was replaced by bromine by
the action of acetyl bromide [24]. Bromide 11 was
obtained in quantitative yield (Scheme 2) and was
treated with dibutyl phosphate 14 in the presence of
ethyl(diisopropyl)amine according to the procedure
508

PHOSPHORYLATED GLYCOCONJUGATES
509
Scheme 1.
O
OH
OH
HO
TsO
TsO
TsO
i
i
ii
iii
iii
OH
OH
OBz
O
OMe
OMe
O
OMe
OMe
O
HO
HO
OMe
OH
OH
OBz
OH
1
2
3
4
O
OH
OH
HO
TsO
OMe
ii
O
O
O
OH OH
OH OH
OBz OBz
OH
5
6
7
8
i: HCl, MeOH, 0–20°C, 24 h; ii: TsCl, Py, 0–20°C, 24 h; iii: BzCl, Py, 0–20°C, 24 h; iv: H2SO4, MeOH, 0–20°C, 24 h.
and a multiplet at 5.75–5.79 ppm due to anomeric
proton of the β-isomer [23]. The signal intensity ratio
was 3.3 in favor of the α-anomer. This is consistent
with the data of [25], according to which the stereo-
selectivity in the glycosylation of dibutyl phosphate 14
depends on the concentration of 2,3,5-tri-O-benzoyl-α-
D-arabinofuranosyl bromide.
described in [25]; the molar ratio 11–(i-Pr)2NEt-–14
was 1:4:4, and the concentration of 11 was 0.003 M
(cf. [25]). Phosphorylated glycoconjugate 15 was
isolated in 29% yield by chromatography (Scheme 3).
The MALDI mass spectrum of 15 displayed a ion peak
with m/z 873.53 [M + Na]+ (C47H63NaO12P, M 873.40).
1
In the H NMR spectrum of 15 we observed a doublet
signal at δ 6.01 ppm with a vicinal coupling constant
of 5.0 Hz due to anomeric proton of the α-anomer [22]
The methoxy group in 12 was quantitatively
replaced by bromine using 33% HBr in AcOH [26].
Scheme 2.
17
Me
Me
13
20
Me
11
16
Me
O
O
1
9
15
7
3
5
ii
4, i
18
19
Me
O
Me
O
O
O
5'
OBz
OBz
O
O
1'
Me
Br
3'
OMe
OBz
OBz
Me
O
10
11
Me
Me
Me COOH
Me
Me
O
O
9
iii
8, i
Me
O
Me
O
O
O
OMe
O
O
Br
OBz OBz
OBz OBz
12
13
i: K2CO3, MeCN, 80°C, 60 h; ii: AcBr, CH2Cl2, 0°C, 3 h; iii: HBr–AcOH, 0°C, 4 h.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 4 2019

SHARIPOVA et al.
510
Scheme 3.
17
Me
13
20
Me
11
16
O
9
1
15
7
3
5
11, ii
18
19
9'
Me
Me
O
6'
O
O
5'
7'
OBz
P
O
O
O
O
1'
13'
Me
3'
11'
OBz
i
15
Me
BuOH + POCl3
(BuO)2P(O)OH
14
Me
O
13, ii
9'
Me
Me
O
6'
O
O
7'
P
O
O
O
O
13'
Me
11'
OBz OBz
16
i: Et3N, toluene, 60°C, 1 h; ii: (i-Pr)2NEt, MeCN, 20°C, 12 h.
Bromide 13 without further purification was treated
with dibutyl phosphate 14 (the reactant ratio was the
same as in the phosphorylation of 11) to obtain 32%
(isolated yield) of phosphorylated glycoconjugate 16
(Scheme 3). The MALDI mass spectrum of 16
contained a ion peak with m/z 873.40 [M + Na]+
MALDI mass spectra were recorded on a Bruker
Daltonik UltraFlex III TOF/TOF instrument operating
in the linear mode (Nd:YAG laser, λ 355 nm; positive
ion detection, a.m.u. range 200–6000; samples were
applied to a metal target from solutions in methanol
with a concentration of 10–3 mg/mL; p-nitroaniline
was used as matrix); the data were processed by
FlexAnalysis 3.0 (Bruker Daltonik, Germany). The
optical rotations were measured at λ 589 nm (20°C) on
a Perkin Elmer-341 polarimeter (USA). The progress
of reactions and the purity of the isolated compounds
were monitored by thin-layer chromatography on
Sorbfil plates (Imid Ltd., Krasnodar, Russia); spots
were visualized by treatment with a 5% solution of
sulfuric acid, followed by heating to 120°C.
1
(C47H63NaO12P, M 873.40). The H NMR spectrum of
16 showed a doublet at δ 6.03 ppm (3J = 5.7 Hz) and
a multiplet at δ 5.73–5.75 ppm due to anomeric
protons of the β- and α-anomers, respectively [23],
with an intensity ratio of 2:1 in favor of the β-anomer.
As far as we know, compounds 15 and 16 are the
first phosphorylated glycoconjugates of terpenoids
with monosaccharides. Study of biological activity of
the synthesized compounds is now in progress.
D-Arabinose and D-ribose were commercial prod-
ucts (Acros, Belgium). Methyl α/β-D-arabinofurano-
side 2, methyl 5-O-p-tosyil-α/β-D-arabinofuranoside 3,
methyl α/β-D-ribofuranoside 6, methyl 5-O-p-tosyl-
α/β-D-ribofuranoside 7, methyl 5-O-p-tosyl-2,3-di-O-
benzoyl-α-D-arabinofuranoside 4, and methyl
5-O-p-tosyl-2,3-di-O-benzoyl-β-D-ribofuranoside 8
were synthesized as described in [21, 27]. The spectral
EXPERIMENTAL
The 1H, 13C, and 31P NMR spectra were recorded on
a Bruker Avance-400 spectrometer (Germany) at 400
1
(1H) and 100.6 MHz (13C, 31P); the H and 13C chem-
ical shifts were measured relative to the residual proton
and carbon signals of the solvent (CDCl3). The
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 4 2019

PHOSPHORYLATED GLYCOCONJUGATES
511
parameters of glycosides 4 and 8 were consistent with
published data [22, 23]. Isosteviol 9 [28] was isolated
from Sweta natural sweetener (Stevian Biotechnology)
according to the procedure reported in [1]. Dibutyl
phosphate 14 was prepared as described in [29].
8.01 m (10H, Harom). 13C NMR spectrum, δC, ppm:
13.82 (C20), 19.43 (C2), 20.31 (C17), 20.79 (C11), 22.14
(C6), 29.44 (C18), 37.80 (C3), 38.29 (C10), 38.50 (C12),
39.91 (C13), 40.24 (C1), 41.93 (C7), 44.41 (C4), 48.93
(C8), 49.15 (C15), 54.78 (C14), 55.21 (C9), 55.98 (C5),
57.67 (OCH3), 65.61 (C5′), 73.24 (C4′), 75.83 (C3′),
79.53 (C2′),107.07 (C1′), 128.76–133.88 (Carom), 165.72
(PhC=O), 165.83 (PhC=O), 177.39 (C19), 222.89
(C16). Mass spectrum, m/z: 695.42 [M + Na]+, 711.41
[M + K]+. Found, %: C 71.35; H 7.22. C40H48O9.
Calculated, %: C 71.41; H 7.19. M 672.80.
5-O-(16,19-Dioxo-ent-beyeran-19-yl)-2,3-di-
O-benzoyl-D-arabinofuranosyl bromide (11). A solu-
tion of 0.3 g (0.48 mmol) of conjugate 10 in 10 mL of
anhydrous methylene chloride was cooled to 0°C,
0.2 mL (2.6 mmol) of acetyl bromide was added, and
0.08 mL (2.1 mmol) of anhydrous methanol in 1 mL of
anhydrous methylene chloride was added dropwise.
The mixture was stirred for 3 h at 0°C, diluted with
20 mL of methylene chloride, and washed with ice
water (2×20 mL) and with a saturated solution of
sodium hydrogen carbonate (2×50 mL). The organic
phase was filtered through a layer of MgSO4, and
the solvent was removed under reduced pressure.
Bromide 11 was isolated in quantitative yield as
a white amorphous powder and was immediately used
in the next stage.
Glycoconjugates 10 and 12 (general procedure).
A solution of 1.08 mmol of methyl 5-O-p-tosyl-2,3-di-
O-benzoyl-α-D-arabinofuranoside 4 or methyl
5-O-p-tosyl-2,3-di-O-benzoyl-β-D-ribofuranoside 8 in
10 mL of acetonitrile was added dropwise with stirring
under argon to a mixture of 1 mmol of isosteviol 9 in
40 mL of acetonitrile and 4 mmol of potassium carbon-
ate. The mixture was refluxed for 20–30 h, the precip-
itate was filtered off, the filtrate was concentrated
under reduced pressure, and the residue was diluted
with water and extracted with chloroform. The extract
was dried over MgSO4, the solvent was distilled off
under reduced pressure, and the residue was subjected
to chromatography on silica gel using petroleum ether–
ethyl acetate at a ratio of 6:1 to isolate conjugate 10 or
at a ratio of 10:1 to isolate conjugate 12. The products
were isolated as white amorphous powders.
Methyl 5-O-(16,19-dioxo-ent-beyeran-19-yl)-2,3-
di-O-benzoyl-α-D-arabinofuranoside (10). Yield
0.33 g (43%), [α]D20 = –53.0° (c = 1, CH2Cl2). 1H NMR
spectrum, δ, ppm: 0.75 s (3H, C20H3), 0.96 s (3H,
C17H3), 1.23 s (3H, C18H3), 0.81–1.95 m (18H), 2.21 d
(1H, 3-Heq, J = 12.9 Hz), 2.62 d.d (1H, 15-Hαx, J =
18.7, 3.7 Hz), 3.47 s (3H, OCH3), 4.32–4.48 m (3H,
4′-H, 5′-H), 5.11 s (1H, 1′-H), 5.44–5.50 m (2H, 2′-H,
3′-H), 7.42–8.08 m (10H, Harom). 13C NMR spectrum,
δC, ppm: 13.19 (C20), 18.74 (C2), 19.68 (C17), 20.16
(C11), 21.51 (C6), 28.74 (C18), 37.15 (C3), 37.71 (C10),
37.87 (C12), 39.26 (C13), 39.63 (C1), 41.32 (C7), 43.80
(C4), 48.23 (C8), 48.51 (C15), 54.15 (C14), 54.59 (C9),
54.81 (C5), 57.03 (OCH3), 63.10 (C5′), 77.55 (C4′),
79.55 (C3′), 82.47 (C2′), 106.69 (C1′), 128.32 (Carom),
129.75 d (Carom), 133.35 d (Carom), 165.33 (PhC=O),
165.47 (PhC=O), 176.73 (C19), 222.13 (C16). Mass
spectrum: m/z 695.29 [M + Na]+. Found, %: C 71.63;
H 7.17. C40H48O9. Calculated, %: C 71.41; H 7.19.
M 672.80.
5-O-(16,19-Dioxo-ent-beyeran-19-yl)-2,3-di-
O-benzoyl-D-ribofuranosyl bromide (13). A solution
of 0.14 g (0.2 mmol) of conjugate 12 in 5 mL of anhy-
drous methylene chloride was cooled to 0°C, 0.3 mL of
a 33% solution of HBr in acetic acid was added, and
the mixture was stirred for 4 h, allowing it to gradually
warm up 20°C. The mixture was poured into 10 mL of
ice water, and the organic phase was separated, washed
with water (2×10 mL), dried over Na2SO4, and
evaporated under reduced pressure. Bromide 13 was
isolated in quantitative yield as a white amorphous
powder and was immediately used in the next stage.
Phosphates 15 and 16 (general procedure).
Bromide 11 or 13, 1 mmol, was dissolved in 50 mL of
anhydrous acetonitrile, and 4 mmol of dibutyl phos-
phate 14 and 4 mmol of ethyl(diisopropyl)amine in
50 mL of anhydrous acetonitrile were added. The
mixture was stirred for 12 h at 20°C under argon, the
solvent was distilled off under reduced pressure, and
the residue was subjected to chromatography on silica
gel using petroleum ether–ethyl acetate (6:1) as eluent
to isolate phosphate 15 or 16 as a transparent oil.
Methyl 5-O-(16,19-dioxo-ent-beyeran-19-yl)-2,3-
di-O-benzoyl-β-D-ribofuranoside (12). Yield 0.16 g
(21%), [α]D20 = –48.0° (c = 0.9, CH2Cl2). H NMR
1
spectrum, δ, ppm: 0.75 s (3H, C20H3), 0.97 s (3H,
C17H3), 1.22 s (3H, C18H3), 0.81–1.96 m (18H), 2.21 d
(1H, 3-Heq, J = 13.5 Hz), 2.64 d.d (1H, 15-Hαx, J =
18.7, 3.7 Hz), 3.46 s (3H, OCH3), 4.23–4.42 m (2H,
5′-H), 4.58–4.62 m (1H, 4′-H), 5.14 s (1H, 1′-H), 5.59–
5.62 m (1H, 2′-H), 5.64–5.69 m (1H, 3′-H), 7.28–
Dibutyl 5-O-(16,19-dioxo-ent-beyeran-19-yl)-2,3-
di-O-benzoyl-α/β-D-arabinofuranosyl phosphate
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 4 2019

SHARIPOVA et al.
512
(15). Yield 0.1 g (29%), [α]D20 = –10.6° (c = 0.5,
CH2Cl2); α/β ratio 3.3. H NMR spectrum, δ, ppm:
76.32 (C3′, β), 79.57 d (C2′, J = 17.1 Hz, β), 80.31 d
(C2′, J = 16.0 Hz, α), 100.50 (C1′, α), 102.43 d (C1′, J =
3.5 Hz, β), 128.53 (Carom), 129.93 (Carom), 133.74
(Carom), 165.03 (PhC=O), 165.44 (PhC=O), 176.92
(C19), 222.45 (C16). 31P NMR spectrum, δP, ppm: –2.81
(β), –0.58 (α). Mass spectrum, m/z: 873.68 [M + Na]+,
889.72 [M + K]+. Found, %: C 66.31; H 7.51; P 3.60.
C47H63O12P. Calculated, %: C 66.34; H 7.46; P 3.64.
M 850.97.
1
0.70 s (3H, C20H3, α), 0.72 s (1H, C20H3, β), 0.90 t (6H,
J = 7 Hz, C9′H3, C13′H3, α), 0.92 t (2H, J = 6.9 Hz,
C9′H3, C13′H3, β), 0.94 s (3H, C17H3, α), 0.95 s (1H,
C17H3, β), 1.19 s (3H, C18H3, α), 1.21 s (1H, C18H3, β),
0.79–1.94 m [33.8H (α) and 0.3H (β), ent-beyerane
skeleton, 7′-H, 8′-H, 11′-H, 12′-H], 2.16-2.22 m (1.6H,
3-Heq), 2.56-2.64 m (1.6H, 15-Hax), 3.94–4.16 m
(5.5H, 6′-H, 10′-H), 4.28–4.46 m (2.9H, 5′-H), 4.61–
4.73 m (1.6H, 4′-H), 5.47–5.49 m (1.6H, 3′-H), 5.59–
5.61 m (1.6H, 2′-H), 5.75–5.79 m (0.3H, 1′-H, β),
6.01 d (1H, J = 5.0 Hz, 1′-H, α), 7.39–8.12 m (13H,
ACKNOWLEDGMENTS
The authors thank the Assigned Spectral–Analytical
Center (Kazan Scientific Center, Russian Academy of
Sciences) for technical support.
H
arom). 13C NMR spectrum, δC, ppm: 13.41 (C20), 13.67
(C9′, C13′), 19.05 (C8′, C12′), 19.96 (C2), 20.42 (C17),
20.44 (C11), 21.75 (C6), 29.01 (C18), 32.41 (C7′), 32.45
(C11′), 37.42 (C3), 38.11 (C10), 38.16 (C12), 39.52 (C13),
39.57 (C1), 41.54 (C7), 44.05 (C4), 48.48 (C8), 48.76
(C15), 54.41 (C14), 54.49 (C9), 54.89 (C5), 57.31 (C5′,
β), 63.19 (C5′, α), 68.02 d.d (C6′, C10′, J = 12.7, 5.9 Hz),
77.24 (C4′, β), 77.83 (C4′, α), 82.16 (C3′, β), 82.28
(C3′, α), 82.66 (C2′, β), 83.19 (C2′, α), 101.07 (C1′, β),
103.05 d (C1′, J = 5.3 Hz, α), 128.63 (Carom), 128.72 d
(Carom), 130.03 d (Carom), 133.92 (Carom), 165.12
(PhC=O), 165.57 (PhC=O), 176.84 (C19), 222.24
(C16). 31P NMR spectrum, δP, ppm: –3.33 (α), –0.68
(β). Mass spectrum: m/z: 873.53 [M + Na]+. Found, %:
C 66.43; H 7.48; P 3.66. C47H63O12P. Calculated, %:
C 66.34; H 7.46; P 3.64. M 850.97.
CONFLICT OF INTERESTS
The authors declare the absence of conflict of
interests.
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α/β ratio 0.5. H NMR spectrum, δ, ppm: 0.71 s (3H,
C20H3, β), 0.73 s (1.5H, C20H3, α), 0.91–0.95 m (9H,
C9′H3, C13H3), 0.96 s (3H, C17H3, β), 0.97 s (1.5H,
C17H3, α), 1.20 s (4.5H, C18H3), 0.82–1.96 m [39H (β)
and 0.5H (α), ent-beyerane skeleton, 7′-H, 8′-H, 11′-H,
12′-H], 2.19 d (1.5H, J = 13.1 Hz, 3-Heq), 2.58–2.69 m
(1.5H, 15-Hax), 4.06–4.16 m (6H, 6′-H, 10′-H), 4.27–
4.54 m (3H, 5′-H), 4.59–4.68 m (1.5H, 4′-H), 5.41–
5.46 m (0.5H, 3′-H, α), 5.60 br.s (1H, 3′-H, β), 5.62–
5.66 m (0.5H, 2′-H, α), 5.73–5.75 m [1.5H, 1′-H (α),
2′-H (β)], 6.03 d (1H, J = 5.7 Hz, 1′-H, β), 7.33–8.01 m
(15H, Harom). 13C NMR spectrum, δC, ppm: 13.49 (C20),
13.67 (C11′, C15′), 18.77, 19.08 (C10′, C14′), 19.98 (C2),
20.00 (C17), 20.45 (C11), 21.79 (C6), 29.03 (C18), 32.34
(C9′, C13′), 37.44 (C3), 38.12 (C10), 38.17 (C12), 39.53
(C13), 39.58 (C1), 41.51 (C7), 44.06 (C4), 48.52 (C8),
48.78 (C15), 54.42 (C14), 54.86 (C9, C5), 57.28 (C5′, β),
64.71 (C5′, α), 67.50 d (C8′, C12′, J = 5.9 Hz), 72.07
(C4′, α), 72.50 (C4′, β), 75.80 d (C3′, J = 9.1 Hz, α),
4. Xu, D., Li, L., Wang, J., Davey, A.K., Zhang, S., and
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