A C14-polyacetylenic glucoside with an α-pyrone moiety and four C10-polyacetylenic glucosides from Mediasia macrophylla

Article abstract of DOI:10.1016/j.phytochem.2009.12.007

Polyacetylenic glucosides (1-5) were isolated from the MeOH extract of Mediasia macrophylla, and their structures were established by spectroscopic analyses. Compounds 2-4 were the first examples of C₁₀-polyacetylenic glucosides found in the family Umbelliferae, while compound 1 was a unique polyacetylenic glucoside possessing an α-pyrone moiety.

Full text of DOI:10.1016/j.phytochem.2009.12.007

Phytochemistry 71 (2010) 688–692
Contents lists available at ScienceDirect
Phytochemistry
journal homepage: www.elsevier.com/locate/phytochem
A C14-polyacetylenic glucoside with an a-pyrone moiety and four
C10-polyacetylenic glucosides from Mediasia macrophylla
Shin-ichiro Kurimoto a, Mamoru Okasaka a, Yoshiki Kashiwada a,
,
*
Olimjon K. Kodzhimatov b, Yoshihisa Takaishi a
a Graduate School of Pharmaceutical Sciences, University of Tokushima, Shomachi 1-78, Tokushima 770-8505, Japan
b Institute of Botany and Botanical Garden, F. Khodzhaev, St. 32, 700143, Tashkent, Uzbekistan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 11 August 2009
Received in revised form 26 October 2009
Available online 13 January 2010
Polyacetylenic glucosides (1–5) were isolated from the MeOH extract of Mediasia macrophylla, and their
structures were established by spectroscopic analyses. Compounds 2–4 were the first examples of C10
polyacetylenic glucosides found in the family Umbelliferae, while compound 1 was a unique polyacety-
lenic glucoside possessing an -pyrone moiety.
-
a
Ó 2009 Elsevier Ltd. All rights reserved.
Keywords:
Mediasia macrophylla
Umbelliferae
Polyacetylene
a-Pyrone
1. Introduction
2. Results and discussion
We have been studying medicinal herbal medicines of Uzbeki-
stan aimed at searching for new natural product leads for thera-
peutic agents (Su et al., 2000a,b,c,d, 2001; Chen et al., 2000; Zhou
et al., 2000; Fu et al., 2001; Tamemoto et al., 2001, 2002; Duan
et al., 2002; Matsuhisa et al., 2002; Shikishima et al., 2002; Tada
et al., 2002; Tanaka et al., 2004; Okasaka et al., 2004, 2006, 2008;
Suzuki et al., 2007). Mediasia macrophylla (Regel ex Schmalh.)
Pimenov (Umbelliferae) is one of the medicinal plants used in
Uzbekistan, whose aerial parts have been used traditionally as a
perfume, an appetite enhancer, a natural preservative, and for
treatment of rheumatism, nephritis, eczema, herpes, and injury
(Chernenko et al., 2002). It is also used in combination with four
other folk medicines for the improvement of hepatic function in
Uzbekistan. Lipids and essential oils are major constituents of M.
macrophylla (Chernenko and Glushenkova, 2003; Baser et al.,
The MeOH extracts of the aerial parts of M. macrophylla (3.9 kg)
were partitioned successively with n-hexane, EtOAc, BuOH, and
H2O. The EtOAc and BuOH soluble fractions were repeatedly sub-
jected to column chromatography to give five new polyacetylenic
glucosides (1–5).
Compound 1 gave IR absorption bands of acetylenic (2227 and
2136 cmꢀ1) and conjugated carbonyl (1700, 1633, and 1558 cmꢀ1
)
groups. The molecular formula of 1 was assigned as C20H22O8 on
the basis of HRESIMS. The 1H NMR spectrum of 1 displayed five ole-
finic protons [dH 7.53 (dd, J = 9.2, 6.8 Hz), 6.37 (dt, J = 16.0, 5.2 Hz),
6.32 (d, J = 6.8 Hz), 6.25 (d, J = 9.2 Hz), and 5.92 (d, J = 16.0 Hz)],
one oxymethyl group [dH 4.46 (ddd, J = 14.8, 5.2, 2.0 Hz) and 4.25
(ddd, J = 14.8, 5.2, 1.6 Hz)], and two methylenes [dH 2.78 (4H, m)], to-
gether with an anomeric proton signal [dH 4.31 (1H, d, J = 7.6 Hz)].
The 13C NMR spectrum showed 20 carbon resonances due to one es-
ter carbonyl carbon (dC 164.8), six olefinic carbons (dC 165.1, 146.2,
144.1, 114.3, 110.9, and 105.4), four quaternary carbon resonances
(dC 82.3, 75.1, 74.7, and 67.2) assignable to acetylenic carbons, and
two methylene carbons (dC 33.3 and 18.0). It also displayed six oxy-
gen-bearing carbon resonances (dC 103.7, 78.0 (2C), 75.0, 71.6 and
62.7), including an anomeric carbon resonance, which coincided
with the presence of a glucosyl moiety, which was confirmed by acid
1997). Quercetin and quercetin-7-O-b-D-galactopyranoside were
also isolated from this plant (Kamilov and Nikonov, 1971). As part
of our study of medicinal plants in Uzbekistan, we have investi-
gated the constituents of M. macrophylla, which resulted in isola-
tion and structure elucidation of
a new C14-polyacetylenic
glucoside with an -pyrone moiety and four new C10-polyacetylen-
a
ic glucosides (2–5). In this paper, we describe the isolation and
structure elucidation of these compounds.
hydrolysis to liberate D
-glucose. The 1H–1H COSY correlations of H-3
(dH 6.25)–H-4 (dH 7.53)–H-5 (dH 6.32), along with the HMBC corre-
lations of H-3 with C-2, H-5 with C-6 and C-10, and of H2-10 with
* Corresponding author. Tel./fax: +81 88 633 7276.
E-mail address: kasiwada@ph.tokushima-u.ac.jp (Y. Kashiwada).
C-2, provided a 6-a
-pyronyl-ethyl moiety. In contrast, the 1H–1H
0031-9422/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.phytochem.2009.12.007

S.-i. Kurimoto et al. / Phytochemistry 71 (2010) 688–692
689
COSY correlations of H-70 (dH 5.92)–H-80 (dH 6.37)–H2-90 (dH 4.46 and
4.25), as well as the HMBC cross-peaks of H-3 with C-2 and of H-5
with C-6, indicated the presence of a 2-propenoxyl moiety. The
geometry of the double bond in the 2-propenoxyl moiety was as-
signed E from the J-value (16 Hz) of the olefinic proton signal. Fur-
ing methylene, and one methyl, along with six carbon resonances
ascribable to a glucosyl moiety (Table 2). The 1H NMR spectrum
of 3 was correlated with that of 2, but showed signals due to a
methyl group [dH 0.90 (3H, t, J = 7.4 Hz)], a methylene [dH 1.59
(2H, m)], and an oxygen-bearing methine [dH 4.18 (1H, t,
J = 6.4 Hz)] instead of the tertiary methyl signal noted for 2. The
connection of these groups was deduced by the 1H–1H COSY corre-
lation of Me-10–H2-9–H-8, together with the HMBC correlations of
H2-9 with C-7, and of H-8 with C-6 and C-5. The location and link-
thermore, the 6-a-pyronyl-ethyl and the 2E-propenoxyl moieties
were shown to be linked through a buta-1,3-diyne moiety from
the HMBC correlations of H2-20 with C-40 and of H-70 with C-50.
The location of the glucosyl moiety was assigned to as C-90 from
the HMBC correlation of H-100 with C-90, while the b-linkage of the
glucosyl moiety was concluded from the coupling constant value
(7.6 Hz) of the anomeric proton signal. On the basis of this examina-
tion, the structure of 1 was proposed as shown (Fig. 1).
Table 1
1H and 13C NMR spectroscopic data for 1 in CD3OD.
Compound 2 also gave an IR absorption band at 2254 cmꢀ1 sug-
gesting it was also an acetylenic derivative. The molecular formula
of 2 was assigned as C16H20O6 by HRESIMS, and its 1H NMR spec-
trum showed the presence of a tertiary methyl group [dH 1.89
(3H, s)], an oxymethyl [dH 3.89 (1H, dt, J = 10.0, 6.0 Hz), 3.58 (1H,
dt, J = 10.0, 6.0 Hz)], and two methylenes [dH 2.41 (2H, t,
J = 7.1 Hz) and 1.78 (2H, m)], together with an anomeric proton sig-
nal [dH 4.19 (1H, d, J = 7.8 Hz)]. The 13C NMR spectrum displayed,
along with six carbon resonances assignable to a glucosyl moiety,
a methyl (dC 3.7), two methylenes (dC 29.6 and 16.6), one oxy-
gen-bearing methylene (dC 69.1), and six quaternary carbon reso-
nances (dC 79.6, 76.2, 66.3, 65.2, 61.2, and 60.2) ascribable to
acetylenic carbons. The 1H–1H COSY correlation of H2-1–H2-2–
H2-3, coupled with the HMBC correlations of Me-10 with C-9, C-
8 and C-7, H2-2 with C-4, and of H2-3 with C-5 and C-6 were indic-
ative of a 4,6,8-decatriynol moiety as an aglycone. The location of
the glucosyl moiety at C-1 was concluded from the HMBC correla-
tion of H-10 with C-1, and the b-linkage was assigned from the J-va-
lue (7.8 Hz) of the anomeric proton signal. Based on these
observations, 2 was assigned as shown in Fig. 1.
Position
1
1Ha
13Cb
1
2
3
4
5
6
10
20
30
40
50
60
70
80
90
–
–
–
164.8
114.3
146.2
105.4
165.1
33.3
18.0
82.3
67.2
75.1
74.7
110.9
144.1
69.4
6.25 (1H, d, 9.2)
7.53 (1H, dd, 9.2, 6.8)
6.32 (1H, d, 6.8)
–
2.78 (2H, m)
2.78 (2H, m)
–
–
–
–
5.92 (1H, d, 16.0)
6.37 (1H, dt, 16.0, 5.2)
4.46 (1H, ddd, 14.8, 5.2, 2.0)
4.25 (1H, ddd, 14.8, 5.2, 1.6)
Glucosyl
1
2
3
4
5
6
4.31 (1H, d, 7.6)
3.24 (1H, dd, 8.8, 7.6)
3.39 (1H, t, 8.8)
3.31 (1H, m)
3.31 (1H, m)
103.7
75.0
78.0
71.6
78.0
62.7
Compound 3 had the molecular formula C16H24O7 on the basis of
HRESIMS. The presence of an acetylenic structure in 3 was indicated
by its IR absorption band (2254 cmꢀ1). The 13C NMR spectrum of 3
exhibited 16 carbon resonances including four acetylenic carbons,
one oxygen-bearing methine, three methylenes, one oxygen-bear-
3.90 (1H, dd, 12.0, 1.6)
3.69 (1H, dd, 12.0, 5.6)
a
d ppm (mult., J in Hz), 400 MHz.
d ppm, 100 MHz.
b
10
9
4
8
8
5
3
2
7
6
2'
OH
5
4
6
O
O
5'
1'
3'
3
8'
6'
4'
9'
7'
1"
1
2
OH
O
OH
O
OH
6"
O
2" OH
5"
O
OH
O
4"
O
OH
HO
HO
HO
HO
HO
HO
3"
1
2
3
8
8
OH
O
O
OH
HO
HO
HO
OH
O
O
OH
OH
HO
HO
4
5
Fig. 1. Structures of acetylenic glucosides (1–5) from M. macrophylla.

690
S.-i. Kurimoto et al. / Phytochemistry 71 (2010) 688–692
Table 2
1H and 13C NMR spectroscopic data for 2–5 in CD3OD.
Position
1
2
3
4
5
1Ha
13Cb
69.1
1Ha
13Cb
69.2
1Ha
13Cb
69.2
1Ha
13Cb
61.3
3.58 (1H, dt, 10.0, 6.0)
3.58 (1H, dt, 10.0, 6.3)
3.57 (1H, m)
3.54 (2H, t, 6.2)
3.89 (1H, dt, 10.0, 6.0)
3.87 (1H, dt, 10.0, 6.1)
3.89 (1H, dt, 10.0, 6.1)
2
3
4
5
6
7
8
9
1.78 (2H, m)
2.41 (2H, t, 7.1)
–
–
–
–
–
–
29.6
16.6
79.6
66.3
60.2
61.2
65.2
76.2
3.7
1.75 (2H, m)
2.36 (2H, t, 7.1)
–
–
–
–
4.18 (1H, t, 6.4)
1.59 (2H, m)
0.90 (3H, t, 7.4)
31.9
16.6
81.2
65.7
69.9
78.0
64.4
29.8
9.8
1.76 (2H, m)
2.39 (2H, t, 7.2)
–
–
–
–
29.7
16.6
81.9
65.5
71.1
75.9
63.9
138.3
116.5
1.65 (2H, m)
2.32 (2H, t, 7.1)
–
–
–
–
32.1
16.3
82.3
65.4
72.2
73.7
70.1
4.77 (1H, m)
5.04 (1H, d, 7.2)
5.84 (1H, ddd, 17.0, 10.1, 5.6)
5.11 (1H, dt, 10.1, 1.3)
5.32 (1H, dt, 17.0, 1.3)
5.79 (1H, ddd, 17.2, 10.1, 7.2)
5.24 (1H, dt, 10.1, 1.1)
5.36 (1H, dt, 17.2, 1.1)
135.5
119.8
10
1.89 (3H, s)
Glucosyl
1
2
3
4
5
6
4.19 (1H, d, 7.8)
3.11 (1H, t, 8.3)
3.29 (1H, m)
3.22 (1H, m)
3.22 (1H, m)
104.5
75.1
78.1
71.6
77.9
61.2
4.17 (1H, d, 7.8)
3.08 (1H, dd, 9.0, 7.8)
3.27 (1H, m)
3.20 (1H, m)
3.19 (1H, m)
104.5
75.1
78.1
71.7
77.9
62.8
4.19 (1H, d, 7.8)
3.10 (1H, dd, 9.0, 7.8)
3.27 (1H, m)
3.20 (1H, m)
3.23 (1H, m)
104.5
75.1
78.1
71.6
77.9
62.7
4.26 (1H, d, 7.8)
3.15 (1H, m)
3.25 (1H, m)
3.23 (1H, m)
3.17 (1H, m)
101.1
74.9
78.1
71.6
78.1
62.8
3.61 (1H, dd, 12.0, 5.1)
3.81 (1H, dd, 12.0, 1.6)
3.59 (1H, dd, 11.8, 5.3)
3.78 (1H, dd, 11.8, 1.9)
3.60 (1H, m)
3.80 (1H, dd, 11.6, 1.9)
3.58 (1H, dd, 12.0, 5.8)
3.78 (1H, dd, 12.0, 2.2)
a
d ppm (mult., J in Hz), 400 MHz.
d ppm, 100 MHz.
b
age of the glucosyl moiety were concluded to be the same as those
of 2 from the HMBC correlation of H-10 with C-1 and J-value (7.8 Hz)
of the anomeric proton signal. From these observations, structure 3
was assigned as shown (Fig. 1).
C10-polyacetylenic glucosides from the family Umbelliferae, while
compound 1 was a structurally unique polyacetylenic glucoside
possessing an
ylenic glucosides (2–5) and a C14-polyacetylenic glucoside with an
a-pyrone moiety (1) suggested that the C14-polyacetylenic unit of
a-pyrone moiety. The co-occurrence of C10-polyacet-
Compounds 4 and 5 possessed the same molecular formula
C16H22O7 on the basis of HRESIMS. They were also polyacetylenic
compounds as deduced from their IR absorption bands
(2254 cmꢀ1 in each case). The 1H- and 13C NMR spectra of 4 and 5
exhibited the presence of the same functional groups, including
one trisubstituted double bond, four acetylenic carbons, one oxy-
gen-bearing methine, one oxygen-bearing methylene, two methyl-
enes, and a glucosyl moiety in each case, indicating that they
possessed the same aglycone moiety. The structure of the aglycone
was assigned as deca-9-en-4,6-diyne-1,8-diol from the 1H–1H COSY
correlation of H2-10–H-9–H-8, and of H2-1–H2-2–H2-3, together
with the HMBC cross-peaks of H-9 with C-7, H-8 with C-6, H2-3
with C-5 and C-6, and of H2-2 with C-4 in each case. The location
of the glucosyl moiety in 4 was concluded to be C-1 from the HMBC
correlation of H-10 with C-1, whereas the HMBC correlation of H-10
with C-8 indicated the location of the glucosyl moiety to be C-8 in 5.
The b-linkage of the glucosyl moiety was assigned from the J-value
(7.7 Hz in each case) of the anomeric proton signals. Based on these
data, the structures of 4 and 5 were assigned as shown (Fig. 1).
Owing to the small amount of the samples for compounds 3–5,
the absolute configurations of C-8 still remain to be determined.
1 may be derived from a C10-polyacetylenic compound, such as the
aglycone of 2, by condensation of the additional two malonyl units,
followed by oxidation.
4. Experimental
4.1. General experimental procedures
Optical rotations were measured with a JASCO DIP-370 digital
polarimeter. MS were obtained on a Waters LCT PREMIER 2695.
IR spectra were recorded on a JASCO FT-IR-420 spectrometer.
NMR (1H NMR: 400 MHz, 13C NMR: 100 MHz, using TMS as int.
stand.) spectra were measured on an AVANCE 400 Fourier trans-
form spectrometer (Bruker). MS were obtained on a LCT PREMIER
(Waters). Column chromatography: silica gel 60 N (63–210 lm,
Kanto Kagaku), Diaion HP-20 (Mitsubishi Chemical), Sephadex
LH-20 (Pharmacia), Toyo pearl HW-40 (TOSOH), MCI-gel: CHP-
20P (75–150
HPLC: ODS [Mightysil RP-18 GP (250 ꢁ 20 mm; 5
ku), CAPCELL PACK C18 SG120 (250 ꢁ 20 mm; 5
COSMOSIL cholester (250 ꢁ 20 mm; 5 m; Nakarai Tesque), COS-
MOSIL m; Nakarai Tesque)], GPC (Gel-
NAP (250 ꢁ 20 mm; 5
Permeation Chromatography) [Asahi pack GS-310 2G (MeOH, Asa-
l
m; Mitsubishi Chemical), YMC-pack ODS-A (YMC).
m; Kanto Kaga-
m; Shiseido),
l
l
l
p
l
3. Concluding remarks
hi KASEI)]. TLC: Merck silica gel 60 F254
.
Five new polyacetylenic glucosides (1–5) were isolated from the
aerial parts of M. macrophylla, and their structures were assigned
by spectroscopic examinations. Polyacetylenic compounds are
widely distributed especially in the families Umbelliferae, Compos-
itae, Araliaceae, and fungi of the group Basidiomycetes. Among
4.2. Plant material
The aerial parts of M. macrophylla were collected at Tashknt re-
gion, Uzbekistan, in July 2002, and were identified by one of authors
(O.K.J.). Herbarium specimens were deposited in the botanical gar-
den of the University of Tokushima (specimen No.: UTP040003).
these, the plants of the family Umbelliferae mainly contain C17
-
polyacetylenic compounds (Christensen and Brand, 2006). By con-
trast, C10- and C14-polyacetylenic glycosides have been reported for
only a few members of the Compositae family (Chang et al., 2005,
2004; Chiang et al., 2007; Kitajima et al., 2003; Li et al., 2004; Park
et al., 2002; Ubillas et al., 2000; Wang et al., 2001; Zhou et al.,
2006) and Campanulaceae (Ishimaru et al., 2003; Yamanaka
et al., 1996). Compounds 2–5 appear to be the first example of
4.3. Extraction and isolation
The aerial parts of M. macrophylla (3.9 kg dry weight) were ex-
tracted three times with MeOH (10 L ꢁ 3) at 60 °C. After removal of

S.-i. Kurimoto et al. / Phytochemistry 71 (2010) 688–692
691
the solvent by evaporation, the MeOH extract (530 g) was succes-
sively partitioned with n-hexane, EtOAc, BuOH, and H2O. The n-
BuOH soluble fraction (77.0 g) was subjected to chromatography
over Diaion HP-20 [MeOH–H2O (0:1 ? 1:0)] to give 12 fractions.
Fraction 7 was further separated by MCI CHP-20P [MeOH–H2O
(3:7 ? 1:0)], and then purified by ODS HPLC (CAPCELL PAK C18
SG120) [MeOH–H2O (2:3)] to yield compound 1 (20 mg).
The EtOAc-soluble fraction (24.0 g) was subjected to silica gel
chromatography using solvents of increasing polarity [n-hexane–
EtOAc–MeOH] to give 27 fractions. Fraction 17 was applied to a
Sephadex LH-20 [MeOH–H2O (3:2 ? 1:0)] column, and then MCI
CHP-20P [MeOH–H2O (1:1 ? 1:0)] to give fractions 17.1–17.4.
Fraction 17.4 was purified by GPC on HPLC (MeOH) to yield com-
pound 2 (9 mg). Fraction 17.2 was further fractionated by GPC on
HPLC (MeOH) into four fractions. Fractions 17.2.2 and 17.2.3 were
separately purified by ODS HPLC (Mightysil RP-18 GP) [MeOH–H2O
(35:65) for fraction 17.2.3; MeOH–H2O (1:1) for 17.2.3] to give
compounds 3 (2 mg) and 4 (1 mg), respectively. Fraction 18 was
fractionated by GPC on HPLC into four fractions. Fraction 18.2
was subsequently purified by silica gel CC [CHCl3–MeOH–H2O
(8:2:0.2)] to yielded compound 5 (1 mg).
1078 cmꢀ1; for 1H and 13C NMR (CD3OD) spectroscopic data, see
Table 2.
References
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4.4. 6-(90-O-b-Glucopyranosyl-non-70-(E)-ene-30,50-diynyl)-pyran-2-
one-3,5-diene (1)
Off white amorphous powder; [
a
]
ꢀ42.6 (MeOH, c 0.3); HRE-
D
SIMS m/z 413.1212 [M+Na]+ (calcd. for C20H22O8Na, 413.1212); IR
(KBr) vmax 3394, 2883, 2227, 2136, 1700, 1633, 1558, 1419, 1363,
1268, 1076, 1033 cmꢀ1; for 1H and 13C NMR (CD3OD) spectroscopic
data, see Table 1.
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4.5. Acid hydrolysis of 1
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Compound 1 (8 mg) was hydrolyzed with 1 m HCl for 8 h at
80 °C. The reaction mixture was diluted with H2O, and extracted
with EtOAc. The aqueous layer was neutralized with Amberlite
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(CC) [CHCl3–MeOH–H2O (7:3:0.5 ? 6:4:1)] to give
4.6. 4,6,8-Decatriynyl b- -glucopyranoside (2)
Pale brown amorphous powder; [
D-glucose.
D
a
]
D
ꢀ18.5 (MeOH, c 0.09);
HRSIMS: m/z 331.1152 [M+Na]+ (calcd. for C16H20O6Na,
331.1158); IR (KBr) vmax 3377, 2902, 2220, 1428, 1373, 1166,
1100, 1076, 1041 cmꢀ1; for 1H and 13C NMR (CD3OD) spectroscopic
data, see Table 2.
4.7. 8-Hydroxy-4,6-decadiynenyl b-
D
-glucoside (3)
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White amorphous powder; [
a
]
D ꢀ10.0 (MeOH, c 0.21); HRSIMS:
m/z 351.1398 [M+Na]+ (calcd. for C16H24O7Na, 351.1420); IR (KBr)
vmax 3419, 2927, 2254, 1637,1419, 1076 cmꢀ1; for 1H and 13C NMR
(CD3OD) spectroscopic data, see Table 2.
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Suzuki, K., Okasaka, M., Kashiwada, Y., Takaishi, Y., Honda, G., Ito, M., Takeda, Y.,
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4.8. Deca-9-en-4,6-diyne-1,8-diol 1-O-b-
D
-glucopyranoside (4)
Pale brown amorphous powder; [
a
]
ꢀ22.9 (MeOH, c 0.11);
D
HRSIMS: m/z 349.1261 [M+Na]+ (calcd. for C16H22O7Na,
349.1263); IR (KBr) vmax 3394, 2922, 2254, 1647, 1078 cmꢀ1; for
1H and 13C NMR (CD3OD) spectroscopic data, see Table 2.
4.9. Deca-9-en-4,6-diyne-1,8-diol 8-O-b- -glucopyranoside (5)
D
Pale brown amorphous powder; [
a
]
ꢀ29.3 (MeOH, c 0.11);
D
HRSIMS: m/z 349.1259 [M+Na]+ (calcd. for C16H22O7Na,
349.1263); IR (KBr) vmax 3410, 2931, 2254, 1618, 1419,

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