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

Phytochemistry 71 (2010) 688–692

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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 b

Graduate School of Pharmaceutical Sciences, University of Tokushima, Shomachi 1-78, Tokushima 770-8505, Japan Institute of Botany and Botanical Garden, F. Khodzhaev, St. 32, 700143, Tashkent, Uzbekistan

a r t i c l e

i n f o

Article history: Received 11 August 2009 Received in revised form 26 October 2009 Available online 13 January 2010 Keywords: Mediasia macrophylla Umbelliferae Polyacetylene a-Pyrone

a b s t r a c t 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 C10polyacetylenic glucosides found in the family Umbelliferae, while compound 1 was a unique polyacetylenic glucoside possessing an a-pyrone moiety. Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction

2. Results and discussion

We have been studying medicinal herbal medicines of Uzbekistan aimed at searching for new natural product leads for therapeutic 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., 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 investigated the constituents of M. macrophylla, which resulted in isolation and structure elucidation of a new C14-polyacetylenic glucoside with an a-pyrone moiety and four new C10-polyacetylenic glucosides (2–5). In this paper, we describe the isolation and structure elucidation of these compounds.

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 subjected to column chromatography to give five new polyacetylenic glucosides (1–5). Compound 1 gave IR absorption bands of acetylenic (2227 and 2136 cm1) and conjugated carbonyl (1700, 1633, and 1558 cm1) groups. The molecular formula of 1 was assigned as C20H22O8 on the basis of HRESIMS. The 1H NMR spectrum of 1 displayed five olefinic 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)], together 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 ester 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 oxygen-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 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 correlations of H-3 with C-2, H-5 with C-6 and C-10 , and of H2-10 with C-2, provided a 6-a-pyronyl-ethyl moiety. In contrast, the 1H–1H

* Corresponding author. Tel./fax: +81 88 633 7276. E-mail address: [email protected] (Y. Kashiwada). 0031-9422/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.phytochem.2009.12.007

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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 assigned E from the J-value (16 Hz) of the olefinic proton signal. Furthermore, 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 examination, the structure of 1 was proposed as shown (Fig. 1). Compound 2 also gave an IR absorption band at 2254 cm1 suggesting it was also an acetylenic derivative. The molecular formula of 2 was assigned as C16H20O6 by HRESIMS, and its 1H NMR spectrum 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 signal [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 oxygen-bearing methylene (dC 69.1), and six quaternary carbon resonances (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, C8 and C-7, H2-2 with C-4, and of H2-3 with C-5 and C-6 were indicative of a 4,6,8-decatriynol moiety as an aglycone. The location of the glucosyl moiety at C-1 was concluded from the HMBC correlation of H-10 with C-1, and the b-linkage was assigned from the J-value (7.8 Hz) of the anomeric proton signal. Based on these observations, 2 was assigned as shown in Fig. 1. 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 cm1). The 13C NMR spectrum of 3 exhibited 16 carbon resonances including four acetylenic carbons, one oxygen-bearing methine, three methylenes, one oxygen-bear-

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 correlation 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-

Table 1 1 H and 13C NMR spectroscopic data for 1 in CD3OD. Position

1 1

13 b

1 2 3 4 5 6 10 20 30 40 50 60 70 80 90

– – 6.25 7.53 6.32 – 2.78 2.78 – – – – 5.92 6.37 4.46 4.25

– 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

Ha

Glucosyl 1 2 3 4 5 6 a b

4.31 3.24 3.39 3.31 3.31 3.90 3.69

6

(1H, (1H, (1H, (1H,

d, 16.0) dt, 16.0, 5.2) ddd, 14.8, 5.2, 2.0) ddd, 14.8, 5.2, 1.6)

(1H, (1H, (1H, (1H, (1H, (1H, (1H,

d, 7.6) dd, 8.8, 7.6) t, 8.8) m) m) dd, 12.0, 1.6) dd, 12.0, 5.6)

1'

8

7

3'

4

5'

5

OH

6

3

8'

6'

4'

9'

OH

4"

6"

5"

HO HO

7'

O

3"

1"

O

OH

OH 2"

HO HO

1

1

O

2

OH

O OH

O

HO HO

3

8

OH

O HO

HO HO

O OH

2

8

OH

O

O OH

O

HO HO

OH 4

103.7 75.0 78.0 71.6 78.0 62.7

10

9 2'

O

(2H, m) (2H, m)

8

5

2

O

(1H, d, 9.2) (1H, dd, 9.2, 6.8) (1H, d, 6.8)

d ppm (mult., J in Hz), 400 MHz. d ppm, 100 MHz.

4 3

C

5

Fig. 1. Structures of acetylenic glucosides (1–5) from M. macrophylla.

OH

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S.-i. Kurimoto et al. / Phytochemistry 71 (2010) 688–692

Table 2 1 H and 13C NMR spectroscopic data for 2–5 in CD3OD. Position

2 1

H

1 2 3 4 5 6 7 8 9 10 Glucosyl 1 2 3 4 5 6 a b

3 a

13 b

C

3.58 3.89 1.78 2.41 – – – – – – 1.89

(1H, (1H, (2H, (2H,

dt, 10.0, 6.0) dt, 10.0, 6.0) m) t, 7.1)

(3H, s)

4.19 3.11 3.29 3.22 3.22 3.61 3.81

(1H, (1H, (1H, (1H, (1H, (1H, (1H,

d, 7.8) t, 8.3) m) m) m) dd, 12.0, 5.1) dd, 12.0, 1.6)

69.1 29.6 16.6 79.6 66.3 60.2 61.2 65.2 76.2 3.7

104.5 75.1 78.1 71.6 77.9 61.2

1

4 a

13 b

H

C

3.58 3.87 1.75 2.36 – – – – 4.18 1.59 0.90

(1H, (1H, (2H, (2H,

dt, 10.0, 6.3) dt, 10.0, 6.1) m) t, 7.1)

(1H, t, 6.4) (2H, m) (3H, t, 7.4)

4.17 3.08 3.27 3.20 3.19 3.59 3.78

(1H, (1H, (1H, (1H, (1H, (1H, (1H,

d, 7.8) dd, 9.0, 7.8) m) m) m) dd, 11.8, 5.3) dd, 11.8, 1.9)

69.2 31.9 16.6 81.2 65.7 69.9 78.0 64.4 29.8 9.8

104.5 75.1 78.1 71.7 77.9 62.8

1

5 a

13 b

H

C

3.57 3.89 1.76 2.39 – – – – 4.77 5.84 5.11 5.32

(1H, (1H, (2H, (2H,

m) dt, 10.0, 6.1) m) t, 7.2)

(1H, (1H, (1H, (1H,

m) ddd, 17.0, 10.1, 5.6) dt, 10.1, 1.3) dt, 17.0, 1.3)

4.19 3.10 3.27 3.20 3.23 3.60 3.80

(1H, (1H, (1H, (1H, (1H, (1H, (1H,

d, 7.8) dd, 9.0, 7.8) m) m) m) m) dd, 11.6, 1.9)

69.2

1

Ha

13 b

C

3.54 (2H, t, 6.2)

29.7 16.6 81.9 65.5 71.1 75.9 63.9 138.3 116.5

1.65 2.32 – – – – 5.04 5.79 5.24 5.36

(2H, m) (2H, t, 7.1)

(1H, (1H, (1H, (1H,

d, 7.2) ddd, 17.2, 10.1, 7.2) dt, 10.1, 1.1) dt, 17.2, 1.1)

104.5 75.1 78.1 71.6 77.9 62.7

4.26 3.15 3.25 3.23 3.17 3.58 3.78

(1H, (1H, (1H, (1H, (1H, (1H, (1H,

d, 7.8) m) m) m) m) dd, 12.0, 5.8) dd, 12.0, 2.2)

61.3 32.1 16.3 82.3 65.4 72.2 73.7 70.1 135.5 119.8

101.1 74.9 78.1 71.6 78.1 62.8

d ppm (mult., J in Hz), 400 MHz. d ppm, 100 MHz.

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). 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 cm1 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 oxygen-bearing methine, one oxygen-bearing methylene, two methylenes, 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. 3. Concluding remarks 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, Compositae, Araliaceae, and fungi of the group Basidiomycetes. Among these, the plants of the family Umbelliferae mainly contain C17polyacetylenic compounds (Christensen and Brand, 2006). By contrast, 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

C10-polyacetylenic glucosides from the family Umbelliferae, while compound 1 was a structurally unique polyacetylenic glucoside possessing an a-pyrone moiety. The co-occurrence of C10-polyacetylenic glucosides (2–5) and a C14-polyacetylenic glucoside with an a-pyrone moiety (1) suggested that the C14-polyacetylenic unit of 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 transform 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: CHP20P (75–150 lm; Mitsubishi Chemical), YMC-pack ODS-A (YMC). HPLC: ODS [Mightysil RP-18 GP (250  20 mm; 5 lm; Kanto Kagaku), CAPCELL PACK C18 SG120 (250  20 mm; 5 lm; Shiseido), COSMOSIL cholester (250  20 mm; 5 lm; Nakarai Tesque), COSMOSIL pNAP (250  20 mm; 5 lm; Nakarai Tesque)], GPC (GelPermeation Chromatography) [Asahi pack GS-310 2G (MeOH, Asahi KASEI)]. TLC: Merck silica gel 60 F254. 4.2. Plant material The aerial parts of M. macrophylla were collected at Tashknt region, Uzbekistan, in July 2002, and were identified by one of authors (O.K.J.). Herbarium specimens were deposited in the botanical garden of the University of Tokushima (specimen No.: UTP040003). 4.3. Extraction and isolation The aerial parts of M. macrophylla (3.9 kg dry weight) were extracted three times with MeOH (10 L  3) at 60 °C. After removal of

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the solvent by evaporation, the MeOH extract (530 g) was successively partitioned with n-hexane, EtOAc, BuOH, and H2O. The nBuOH 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 compound 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). 4.4. 6-(90 -O-b-Glucopyranosyl-non-70 -(E)-ene-30 ,50 -diynyl)-pyran-2one-3,5-diene (1) Off white amorphous powder; [a]D 42.6 (MeOH, c 0.3); HRESIMS 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 cm1; for 1H and 13C NMR (CD3OD) spectroscopic data, see Table 1. 4.5. Acid hydrolysis of 1 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 IRA-40 resin and was purified by silica gel column chromatography (CC) [CHCl3–MeOH–H2O (7:3:0.5 ? 6:4:1)] to give D-glucose. 4.6. 4,6,8-Decatriynyl b-D-glucopyranoside (2) Pale brown amorphous powder; [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 cm1; for 1H and 13C NMR (CD3OD) spectroscopic data, see Table 2. 4.7. 8-Hydroxy-4,6-decadiynenyl b-D-glucoside (3) 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 cm1; for 1H and 13C NMR (CD3OD) spectroscopic data, see Table 2. 4.8. Deca-9-en-4,6-diyne-1,8-diol 1-O-b-D-glucopyranoside (4) Pale brown amorphous powder; [a]D 22.9 (MeOH, c 0.11); HRSIMS: m/z 349.1261 [M+Na]+ (calcd. for C16H22O7Na, 349.1263); IR (KBr) vmax 3394, 2922, 2254, 1647, 1078 cm1; for 1 H and 13C NMR (CD3OD) spectroscopic data, see Table 2. 4.9. Deca-9-en-4,6-diyne-1,8-diol 8-O-b-D-glucopyranoside (5) Pale brown amorphous powder; [a]D 29.3 (MeOH, c 0.11); HRSIMS: m/z 349.1259 [M+Na]+ (calcd. for C16H22O7Na, 349.1263); IR (KBr) vmax 3410, 2931, 2254, 1618, 1419,

1078 cm1; for 1H and Table 2.

13

C NMR (CD3OD) spectroscopic data, see

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