Chemical constituents of Trachelospermum jasminoides

Article abstract of DOI:10.1080/14786410903244962

Ten compounds, comprising a new C₈ normonoterpenoid glycoside, trachelinoside (1), structurally as 4-(2-O-β-D-glucopyranosyl)- hydroxyethyl-5,5-dimethyldihydrofuran-2(3H)-one, together with nine known compounds, were isolated from the 85% ethanol extract of the vines and leaves of Trachelospermum jasminoides (Lindl.) Lem.

Full text of DOI:10.1080/14786410903244962

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Chemical constituents of
Trachelospermum jasminoides
Xing-Qi Tan a b , Liang-Jun Guo a , Yi-Hua Qiu a , Hai-Sheng Chen b
& Chang-Heng Tan c
a PLA 98th Hospital , Huzhou 313000, China
b College of Pharmacy, Second Military Medical University ,
Shanghai 200433, China
c Department of Natural Medicinal Chemistry , Shanghai Institute
of Materia Medica, CAS , Shanghai 201203, China
Published online: 19 Jul 2010.
To cite this article: Xing-Qi Tan , Liang-Jun Guo , Yi-Hua Qiu , Hai-Sheng Chen & Chang-Heng
Tan (2010) Chemical constituents of Trachelospermum jasminoides , Natural Product Research:
Formerly Natural Product Letters, 24:13, 1248-1252, DOI: 10.1080/14786410903244962
To link to this article: http://dx.doi.org/10.1080/14786410903244962
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Natural Product Research
Vol. 24, No. 13, 15 August 2010, 1248–1252
Chemical constituents of Trachelospermum jasminoides
Xing-Qi Tanab, Liang-Jun Guoa, Yi-Hua Qiua, Hai-Sheng Chenb
*
c
*
and Chang-Heng Tan
b
aPLA 98th Hospital, Huzhou 313000, China; College of Pharmacy, Second Military
Medical University, Shanghai 200433, China; cDepartment of Natural Medicinal Chemistry,
Shanghai Institute of Materia Medica, CAS, Shanghai 201203, China
(Received 18 April 2009; final version received 11 August 2009)
Ten compounds, comprising a new C8 normonoterpenoid glycoside,
trachelinoside (1), structurally as 4-(2-O-ꢀ-D-glucopyranosyl)-hydroxy-
ethyl-5,5-dimethyldihydrofuran-2(3H)-one, together with nine known
compounds, were isolated from the 85% ethanol extract of the vines and
leaves of Trachelospermum jasminoides (Lindl.) Lem.
Keywords: Trachelospermum jasminoides; Apocynaceae; trachelinoside
1. Introduction
The vines of Trachelospermum jasminoides (Lindl.) Lem. (Apocynaceae) are a
common traditional Chinese medicine for the treatment of rheumatic arthralgia,
aching of the waist and knee and traumatic injuries (Tu, Fang, & Yuan, 1992).
Previous phytochemical investigations have disclosed that triterpenoids (Tan, Chen,
Zhou, & Zhang, 2006), lignans (Tan et al., 2005), alkaloids (Fatima, Crank, & Wasti,
1988; Fatima, Ijaz, Crank, & Wasti, 1987) and flavanoids (Fu, Zhao, Wang, & Yu,
2008) can be isolated from the title plant. As a continuation of our investigation of
phytochemicals from T. jasminoides (Tan et al., 2005, 2006), we re-examined the
chemical constituents of the 85% EtOH extract and obtained a new C8
normonoterpenoid glycoside named trachelinoside (1), structurally as 4-(2-O-ꢀ-D-
glucopyranosyl)-hydroxyethyl-5,5-dimethyldihydrofuran-2(3H)-one, together with
four megastigmane glycosides: (6R,9R)-3-oxo-ꢁ-ionol-ꢀ-D-apiofuranosyl-(1 ! 6)-
ꢀ-D-glucopyranoside (2), roseoside (3), icariside B5 (4) and actinidioionoside (5);
four aromatic compounds: sodium ferulate (6), salicylic acid (7), vanillic acid (8) and
benzenyl methanol ꢀ-D-glucopyranoside (9), as well as dambonitol (10). Compounds
2–9 were isolated from this genus for the first time.
2. Results and discussion
Compound 1, obtained as a white amorphous powder, had the molecular formula
C14H24O8, as deduced from the HRESIMS quasi-molecular ion peak at m/z 343.1368
*Corresponding authors. Emails: haishengc@hotmail.com; chtan@mail.shcnc.ac.cn
ISSN 1478–6419 print/ISSN 1029–2349 online
ß 2010 Taylor & Francis
DOI: 10.1080/14786410903244962
http://www.informaworld.com

Natural Product Research
1249
([M þ Na]þ, C14H24O8Na requires 343.1369). The IR adsorption at 1784 cmꢀ1
,
proton signals of a methylene (ꢂH 2.61 and 2.49, each dd, Jgeminal ¼ 16.8 Hz) and
carbon signal at ꢂC 175.4, suggested the presence of a five-member lactone ring. The
carbon resonances at ꢂC 102.6, 78.0, 76.9, 75.2, 71.6 and 61.1, as well as an anomeric
proton signal at ꢂH 4.12 (d, J ¼ 8.0 Hz) combined with the hydrolysis experiment
indicated a ꢀ-D-glucopyranosyl as the sugar moiety (Agrawal, 1992).
In addition to those protons and carbons due to the glucose, its 1H and 13C NMR
spectra showed signals for two tertiary methyls (ꢂH 1.37 and 1.19), three methylenes
(ꢂC 67.1, 34.2 and 28.9), one methine (ꢂC 42.1 and ꢂH 2.33), one oxygen-bearing
quaternary carbon (ꢂC 86.1) and one carbonyl group (ꢂC 175.4). The HMQC and
1H–1H COSY spectra exhibited a proton spin system of –CH2–CH2–CH–CH2–
(Figure 1). The terminal methylenes were determined to be connected with the
glucosyloxyl and the carbonyl, respectively, by HMBC correlations (Figure 1). The
quaternary carbon was assigned to be linked with the methine of the fragment and
the O-atom of the lactone to form the five-member lactone ring. Therefore, the
structure of trachelinoside (1) was strictly proven to be 4-(2-O-ꢀ-D-glucopyranosyl)-
hydroxyethyl-5,5-dimethyldihydrofuran-2(3H)-one. This is the first report of a
monoterpene glycoside from this genus.
Subramanian and Krishna Rao (1967) reported a similar structure, ethyl (ꢀ)-
terpenylate
(ethyl
tetrahydro-2,2-dimethyl-5-oxo-3-furanacetic
acid,
Vb
therein), which was synthesised starting from ꢁ-pinene via pinonic acid.
It suggested that 1 might be biogenetically transformed from a monoterpenoid.
Furthermore, the aglycone of 1 had been also synthesised through a photo-
chemical alkylation of 5,6-dihydro-2-pyrone with Me2CHOH by Guzman and
Mendoza (1981).
The known compounds were identified to be (6R,9R)-3-oxo-ꢁ-ionol-ꢀ-D-
apiofuranosyl-(1 ! 6)-ꢀ-D-glucopyranoside (2) (De Tommasi, Aquino, De Simone,
& Pizza, 1992), roseoside (3) (De Tommasi et al., 1992), icariside B5 (4) (Miyase,
Ueno, Takizawa, Kobayashi, & Oguchi, 1988), actinidioionoside (5) (Otsuka,
Hirata, Shinazato, & Takeda, 2003), sodium ferulate (6), salicylic acid (7), vanillic
acid (8) (Chen, Wu, & Ryan, 2002), benzenyl methanol ꢀ-D-glucopyranoside (9)
(Seiglera, Pauli, Nahrstedt, & Leen, 2002), and dambonitol (10) (Shima, Hisada, &
Inagaki, 1972) by optical rotation, 1H, 13C NMR and MS analysis, and comparisons
with literature data and/or authentic samples.
7
HO
6
OGlu(6–1)Api
8
5
R
O
O
9
HO
HO
1'
4
O
OH
2
H
3
1H–1H COSY
O
O
HMBC (H to C)
2 R = H
1
3 R = OH
Figure 1. The structures of 1–3 and significant 2D NMR correlations of 1.

1250
X.-Q. Tan et al.
3. Experimental
3.1. General experimental procedures
Optical rotations were measured on a Perkin–Elmer 343 polarimeter. IR spectra were
recorded on a Bruker Vector 22 (KBr). All mass data were obtained with a Q-Tof
micro mass spectrometer. NMR spectra were recorded on a Bruker DRX-500
instrument. The chemical shift values are reported in units (ꢂ) and coupling constants
(J) are given in Hertz. Silica gel (200–300 mesh), macroporous resin (AB-8, Tianjin
Zheng-Tian-Cheng Clarify Technology Co. Ltd, Tianjin, China), Sephadex LH-20
(Pharmacia Biotech AB, Uppsala, Sweden) and ODS-A gel (Greenberbs Science &
Technology Development Co. Ltd, Beijing, China) were used for column chroma-
tography (CC) and precoated plates of silica gel (HSGF254) were used for for TLC.
3.2. Plant material
The fresh stems with leaves of Trachelospermum jasminoides (Lindl.) Lem. were
collected in Daochang Mountain, Zhejiang Province, China, in November 2001 and
identified by Prof. Han-Cheng Zheng of the Second Military Medical University.
A voucher specimen (20010511027) was deposited in the Herbarium of the
Department of Pharmcognosy, Second Military Medical University.
3.3. Extraction and isolation
Fifteen kilograms of dried vines and leaves of T. jasminoides were powdered, and
extracted thrice with 85% EtOH, the combined extraction was concentrated under
reduced pressure, then diluted with distilled water to 2 L, finally subjected to a
chromatography of macroporous resin column (18 ꢁ 100 cm), eluting with H2O, 20,
40, 60 and 95% EtOH, to yield frs 1–5. Fr. 2 (150 g) was separated into five
subfractions: frs 2a–e by silica gel CC (the lower layer of CHCl3 : MeOH : H2O
65 : 10 : 10 as eluent). Frs 2b and 2c yielded 1 (19 mg), 3 (8 mg), 4 (12 mg), 5 (19 mg)
and 7 (42 mg), as well as 2 (22 mg) and 6 (31 mg), respectively, after repeated
purification through silica gel (eluent ditto), Sephadex LH-20 (MeOH–H2O,
50–100%) and Rp-18 (MeOH–H2O, 30–50%) columns. Fr. 4 (70 g) gave 9 (14 mg)
and 10 (290 mg), and fr. 5 (30 g) yielded 8 (110 mg) after repeated CCs of silica gel,
Sephadex LH-20 and Rp-18.
3.4. Trachelinoside (1)
White powder, [ꢁ]2D1 ꢀ 13.5 (c 0.347, MeOH); IR (KBr) ꢃmax: 3372, 1784, 1380, 1278,
1
1261, 1167, 1030 cmꢀ1; H NMR data: (DMSO-d6, 500 MHz): ꢂ 4.94 (1H, br s,
20-OH), 4.91(1H, br s, 40-OH), 4.88 (1H, br s, 30-OH), 4.44 (1H, br t, J ¼ 6.0 Hz,
60-OH), 4.12 (1H, d, J ¼ 8.0 Hz, H-10), 3.75 (1H, dt, J ¼ 10.0, 7.0 Hz, H-9a), 3.67 (1H,
br dd, J ¼ 12.0, 2.8 Hz, H-60a), 3.50 (1H, dt, J ¼ 10.0, 7.0 Hz, H-9b), 3.43 (1H, dt,
J ¼ 12.0, 5.8 Hz, H-60b), 3.13 (1H, t, J ¼ 8.0 Hz, H-30), 3.09 (1H, ddd, J ¼ 8.8, 5.5,
2.3 Hz, H-50), 3.03 (1H, br t, J ¼ 8.8 Hz, H-40), 2.94 (1H, br t, J ¼ 8.0 Hz, H-20), 2.61
(1H, dd, J ¼ 16.8, 7.8 Hz, H-3a), 2.49 (1H, dd, J ¼ 16.8, 11.9 Hz, H-3b), 2.33 (1H,
dtd, J ¼ 12.0, 7.2, 3.7 Hz, H-4), 1.73 (1H, dtd, J ¼ 12.1, 7.3, 4.1 Hz, H-8a), 1.50

Natural Product Research
1251
(1H, dq, J ¼ 12.2, 7.5 Hz, H-8b), 1.37 (3H, s, Me-6), 1.19 (3H, s, Me-7); 13C NMR
data: (DMSO-d6, 125 MHz): C¸ 175.4 (C-2), 102.6 (C-10), 86.1 (C-5), 76.8 (C-50), 76.7
(C-30), 73.3 (C-20), 70.1 (C-40), 67.1 (C-9), 61.1 (C-62), 42.1 (C-4), 34.2 (C-3), 26.9
(C-6), 28.9 (C-8), 21.6 (C-7),. ESI-MS: m/z 343 ([M þ Na]þ), 359 ([M þ K]þ) and 663
([2M þ Na]þ). HR-ESI-MS: m/z 343.1368 ([M þ Na]+), Calcd. for C14H24O8Na,
343.1369.
3.5. Acid hydrolysis of 1
A solution of 1 (2 mg) in 2 M HCl : dioxane (1 : 1, v/v, 2 mL) was heated under reflux
for 2 h. After cooling, the reaction mixture was neutralised with NaHCO3, then
filtrated to remove the solid. The solution was subjected to CC (Sephadex LH-20,
MeOH : H2O 1 : 1) to afford a sugar fraction. The sugar fraction and standard
D-glucose (Sigma, USA) were respectively treated with L-cysteine methyl ester
hydrochloride (2 mg) in pyridine (1 mL) at 60ꢂC for 1 h; then the solution was treated
with N,O-bis(trimethylsilyl)-trifluoroacetamide (0.02 mL) at 60ꢂC for 1 h, after
subjecting the supernatant to GLC analysis (Supelco, 230ꢂC, flow rate:
15 mL minꢀ1). D-Glucose (standard: tR ¼ 23.9 min, 1: tR ¼ 24.0 min) was detected.
Acknowledgement
This project was supported by grants from the Natural Science Fund of Huzhou (2004–20).
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