Triptergosidols A-D, nerolidol-type sesquiterpene glucosides from the leaves of Tripterygium wilfordii

Article abstract of DOI:10.1016/j.fitote.2018.05.018

Four new nerolidol-type sesquiterpene glucosides, triptergosidols A-D (1-4) were isolated from the leaves of Tripterygium wilfordii. Three aglycones, named triptergerols A (1a), B (2a), and C (3a), were acquired by enzymatic hydrolysis of 1-3. The structu

Full text of DOI:10.1016/j.fitote.2018.05.018

Fitoterapia 128 (2018) 187–191
Contents lists available at ScienceDirect
Fitoterapia
journal homepage: www.elsevier.com/locate/fitote
Triptergosidols A-D, nerolidol-type sesquiterpene glucosides from the leaves
of Tripterygium wilfordii
a,b
a
b
a
a
a
a,⁎
Lin Ni , Li Li , Yatie Qiu , Fang-You Chen , Chuang-Jun Li , Jie Ma , Dongming Zhang
a
State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Chinese Academy of Medical Sciences and Peking Union Medical College, Institute of
Materia Medica, Beijing 100050, China
b
College of Plant Protection, Fujian Agriculture and Forestry University, Fuzhou 350002, Fujian Province, China
A R T I C L E I N F O
A B S T R A C T
Keywords:
Four new nerolidol-type sesquiterpene glucosides, triptergosidols A-D (1-4) were isolated from the leaves of
Tripterygium wilfordii. Three aglycones, named triptergerols A (1a), B (2a), and C (3a), were acquired by enzy-
matic hydrolysis of 1-3. The structures of nerolidol-type sesquiterpenes were elucidated on base of kinds of
spectroscopic analysis, and their absolute configurations were determined by CD method. In addition, com-
pounds 1-4 were tested for cytotoxicity against two cell lines and inhibitory effects against NO production in
RAW264.7 macrophage.
Tripterygium wilfordii
Sesquiterpene glucosides
Aglycone
Anti-inflammation
1. Introduction
77.9 (C-5′), 62.7 (C-6′)] and 15 carbons of aglycone moiety. The
aglycone contained four tertiary methyls [δ
each, all s, H-12, 13, 14, and 15)], a vinyl ABX system at δ
d, J = 10.8 Hz, H-1a), 5.21 (1H, dd, J = 17.4, 1.5 Hz, H-1b), 5.96 (1H,
dd, J = 17.4, 10.8 Hz, H-2), a trans-double bond at δ 5.63 (1H, m, H-5)
and 6.14 (1H, d, J = 15.5 Hz, H-6), a olefin proton at δ 5.71 (1H, m, H-
8), one oxygenated methine at δ 3.64 (1H, m, H-10), together with two
H
1.78, 1.24, 1.22, 1.20 (3H
Tripterygium wilfordii Hook.f. (TWHF) is one of species in the genus
H
5.04 (1H, br
tripterygium, which has been used widely in traditional medicine [1], for
treatment of inflammation [2], psoriasis, systemic lupus erythematosus,
ankylosing spondylitis, and idiopathic IgA nephropathycancer in China
H
H
[
3]. TWHF has attracted great attention for natural product research
H
during the last five decades, which have contributed more than 200
new compounds so far, including alkaloids [4,5], triterpenoids [6],
diterpenes [7], sesquiterpenes [8], megastigmane glycosides [9], fla-
vanones [10] and lignans [11]. We have been working on the sig-
nificant bioactivities leaves of TWHF, and four new nerolidol-type
sesquiterpene glucosides (Fig. 1) were acquired. Notably, their agly-
cons, triptergerol A-C (1a-3a, Fig. 1), which were liberated by Hydro-
lysis of 1-3 with snailase, were also new compounds. Herein we report
the isolation, structure elucidation, and biological activities of them.
methylenes, and two quaternary carbons. Compound 1 was deduced to
be a noncyclic sesquiterpene glycoside to meet the requirement of un-
saturation degrees on the basis of the above analysis. As shown in
Fig. 2, the 1He H COSY experiment on 1 indicated the presence of a
partial structure, written in bold lines, and in the HMBC experiment
(Fig. 2), long range correlations were observed between the following:
1
H
3
-12 and C-10 (δ
129.3); H -14 and C-6 (δ
146.4), C-3 (δ 73.9), C-4. HMBC correlations from H-10 (δ
C-1′ (δ 103.9); from H-1′ [δ 4.38 (1H, d, J = 6.8 Hz] to C-10 (δ
suggested that the glucose was connected to C-10.
The relative stereostructure of 1 was characterized by the NOE
measurement and coupling constant (Fig. 3). Irradiation of H -14 en-
hanced the signal at H-5, and H-6 enhanced the signal H-8, and no NOE
was observed between H-8 and H -14. Thus, it was proven that H-5 and
-14 were on the same side, and H-6 and H-8 was on the other side.
The relative configuration of double bonds between C-5 and C-6 was
C
87.8), C-11 (δ
C
73.6); H-6 and C-4 (δ
C
47.0), C-8 (δ
C
3
C
139.1), C-7 (δ
C
135.5), C-8; H
3
-15 and C-2 (δ
C
C
H
3.64, m) to
87.8)
C
H
C
2
. Results and discussion
Triptergosidol A (1) was obtained as colorless oil with a molecular
3
formula of C21
H
36
O
8
, based on HRESIMS analysis (m/z 439.2316
M + Na] , calcd for 439.2302). The molecular formula accounted for
four indices of hydrogen deficiency. The IR spectrum of 1 showed ab-
+
[
3
H
3
−
1
sorption bands at 3380 and 1645 cm
double bond functions, respectively. The H and C NMR (Table 1)
4.38 (1H, d,
103.9 (C-1′), 75.3 (C-2′), 78.1 (C-3′), 71.6 (C-4′),
ascribable to hydroxyl and
1
13
H
deduced as E by the coupling constant [δ 6.14 (1H, d, J = 15.5 Hz, H-
6)].
spectra of 1 showed signals assignable to 1 β-glucose [δ
H
J = 6.8 Hz, H-1′); δ
C
Hydrolysis of 1 with snailase gained its aglycone (1a) and glucose.
⁎
Corresponding author.
E-mail address: zhangdm@imm.ac.cn (D. Zhang).
https://doi.org/10.1016/j.fitote.2018.05.018
Received 26 April 2018; Received in revised form 15 May 2018; Accepted 16 May 2018
Available online 17 May 2018
0367-326X/ © 2018 Published by Elsevier B.V.

L. Ni et al.
Fitoterapia 128 (2018) 187–191
employing to identify the absolute configuration to the C-3 and C-10.
Due to the presence of a 10,11-diol, the absolute configuration of 1 at
the C-10 carbon could be ascertained through CD analysis using
Mo
in the induced circular dichroism of 1-[Mo
Fig. 4). According to Snatzke's method, the absolute configurations of
2
(OAc)
4
[12,13]. The observed sign of the diagnostic band at 318 nm
2
(OAc) ] was positive
4
(
C-10 was determined to be S. And the 10S absolute configuration
showed a positive cotton effect at 230 nm in the CD spectrum. The S
absolute configuration at the C-3 of compound 1 has deduced using
double bonds of the CD helicity rule [14,15]. Since the CD spectrum of
1
showed a positive cotton effect at 200 nm, the 3-position was de-
termined to be S configuration.
Therefore, the structure of 1 was identified as (3S,5E,7E,10S)-10-β-
-glucopyranosyloxy-3,11-dihydroxy-3,7,11-trimethyldodeca-1,5,7-
D
Fig. 1. The structures of compounds 1-4 and 1a-3a.
triene, named triptergosidol A. Its aglycon, also was a new compound,
named triptergerol A.
Table 1
Triptergosidol B (2) was obtained as colorless oil. Its molecular
formula, C21H O , was the same as 1, as determined by HR-ESI-MS.
36 8
1
H and 13C NMR spectrosopic data assignments for 1 and 1a.
NO.
1a
1ab
The NMR data of 2 were similar to those of 1 except C-10 (Table 2).
These data suggested that 2 was an analogue of 1 eith different con-
figuration at C-10, which was further confirmed by CD spectrum. The
CD spectrum of 2 showed a negative cotton effect at 214.5 nm (Fig. 5),
the 10-position was determined to be R configuration. Its aglycon,
which was liberated by Hydrolysis of 2 with snailase(Table 3), was also
a new compound, named triptergerol B (2a).
Triptergosidol C (3) as obtained as colorless oil which exhibited the
molecular ion peak at m/z 439.2316 [M + Na]+ as the base peak in the
HRESIMS spectrum. Its molecular formula was determined to be
1
1
2
3
4
5
6
7
8
9
9
1
1
1
1
1
1
1
2
3
4
5
6
a
b
5.04 (d, 10.8)
5.21 (d,17.4)
5.96 (dd, 17.4, 10.8)
112.0
5.03 (dd,10.8, 1.5)
5.20 (dd,17.4, 10.8)
5.95 (dd,17.4, 10.8)
112.0
146.4
73.9
146.4
73.9
47.0
123.4
139.2
135.8
129.8
31.3
2.32 (m)
47.0
2.31 (m)
5.63 (m)
6.14 (d,15.5)
123.7
139.1
135.5
129.3
31.1
5.61 (m)
6.12 (d,15.5)
5.71 (m)
2.32 (m)
2.52 (m)
3.64 (m)
5.56 (t,7.1)
2.15 (m)
2.50 (m)
3.40 (m)
a
b
0
1
2
3
4
5
′
′
′
′
′
C
21
H
36
O
8
, the same as for 1 and 2. A detailed comparison of NMR data
revealed that 3 is differed from 2 mainly at C-7 and C-8 (Table 2). NOE
correlations of H-8 and 7-CH confirmed the cis- configurations for
87.8
73.6
26.3
25.1
12.8
27.2
103.9
75.3
78.1
71.6
77.9
62.7
79.8
73.7
25.9
24.8
12.9
27.1
3
1.20 (s)
1.22 (s)
1.78 (s)
1.24 (s)
4.38 (d,6.8)
3.23 (m)
3.23 (m)
3.31 (m)
3.38 (m)
3.66 (m),3.87 (m)
1.21 (s)
1.18 (s)
1.76 (s)
1.24 (s)
double bond between C-7 and C-8. Therefore, the structure of 1 was
identified as (3S,5E,7Z,10R)-10-β-D-glucopyranosyloxy-3,11-dihy-
droxy-3,7,11-trimethyldodeca-1,5,7-triene, named triptergosidol C. Its
aglycon, also was a new compound, named triptergerol C (Table 3).
Triptergosidol D (4) was obtained as colorless oil. Its molecular
formula, C21
ESI-MS. The NMR data of 4 were similar to those of 3 except C-10
Table 2). These data suggested that 4 was an analogue of 3 with dif-
36 8
H O , was the same as 1, 2, and 3, as determined by HR-
′
(
ferent configuration at C-10, which was further confirmed by CD
spectrum. The CD spectrum of 4 showed a positive cotton effect at
240.5 nm (Fig. 5), the 10-position was determined to be S configura-
tion.
δ in ppm; J in Hz within parentheses.
a
b
Measured at 500 MHz for H NMR and 125 MHz for 13C NMR in CD
1
3
OD.
Measured at 600 MHz for 1H NMR and 150 MHz for 13C NMR in CD
3
OD.
Four nerolidol-type sesquiterpene glucosides were evaluted for cy-
totoxic activities against A549 and Hela, and no compounds showed
obvious activity at a concentration of 50 μM. Compounds 1 and 2 ex-
hibited inhibitory effects with inhibition ratio value of 65.2 ± 7.3%
and 58.2 ± 5.6% at concentration 60 μM against NO production in
LPS-induced RAW264.7 macrophage.
3. Experimental section
Fig. 2. Key 1He H COSY and HMBC correlations of 1.
1
3.1. General experimental procedures
Optical rotation was performed in a JASCO P2000 automatic digital
polarization device, which is from Tokyo, Japan. The CD spectra were
performed on the JASCO J-815 CD spectrometer. The UV spectra were
measured on JASCO v-650 spectrophotometer and IR spectra were
carried out a Nicolet 5700 spectrometer (thermal electron, Madison,
USA). The NMR spectra were obtained by the AV-600-III spectrometer
Fig. 3. Key 1D-NOE correlations of 1 and 3.
(
Bruker, USA) and INOVA-500 (Varian, palo Alto, California, USA).
HRESIMS spectra were recorded an Agilent 1100 series LC/MSD ion
trap mass spectrometer (Agilent, Waldbronn, Germany). HPLC was
prepared using the Shimadzu LC-6AD instrument with SPD-20A de-
tector(Shimadzu, Kyoto, Japan) and YMC -pack ODS (YMC, 250 × 20
mm, 5 μm Kyoto). Using silica gel (200–300 mesh) and polyamide
The glucose was purified by column chromatography over silica gel and
determined to D-(+)-glucose by comparison their optical rotation {D-
2
5
(
+)-glucose had positive optical rotation ([α]
D
+ 42.3), and the op-
2
5
tical rotation of glucose is [α]
D
+ 48.3}. Two different methods was
188

L. Ni et al.
Fitoterapia 128 (2018) 187–191
Fig. 4. CD spectrum of compound 1a in a DMSO of dimolybdenum tetraacetate (the inherent CD of the diol was subtracted).
Table 2
3.2. Plant material
1
H and 13C NMR spectrosopic data assignments for 2-4.
The leaves of T. wilfordii were collected in Shanming, Fujian
Province, People's Republic of China (PRC), in September 2009 and
identified by Professor Lin Ma from the Institute of Materia Medica
NO.
2
3
4
1
1
2
a
5.04 (br.d,10.8)
5.21 (dd,17.3,1.5)
5.96
112.0 5.05 (dd,
112.1 5.05 (dd, 10.8, 112.1
1
0.8, 1.3)
5.21 (dd,
7.4, 1.3)
1.5)
5.22 (dd, 17.4,
1.5)
(
IMM), Chinese Academy of Medical Sciences and Peking Union
b
Medical College (CAMS & PUMC). A voucher specimen (No. 20090034)
is deposited at the herbarium of the IMM, CAMS & PUMC, PRC.
1
146.4 5.96 (dd,
17.4, 10.8)
74
146.3 5.97 (dd, 17.4, 146.4
10.8)
(
dd,17.4,10.8)
3
4
5
73.9
47.3
73.9
47.3
3.3. Extraction and isolation
2.33 (m)
5.59 (td,15.6,7.5)
47
123.8 5.72 (dt,
5.6, 7.5)
139.3 6.49 (d,
5.6)
2.37 (m)
2.37 (m)
126.6 5.77 (dt, 15.6, 127.2
7.5)
1
After drying at room temperature, the leaves of T. wilfordii (100 kg)
6
6.17 (d,15.6)
131.6 6.52 (dt,15.6)
131.2
were pulverized and refluxed with EtOH-water (80:20, v/v,
00 L × 2 h × 3). Solvent was evaporated in vacuo, and the fluid extract
1
4
7
8
9
9
1
134.9
129.9 5.66 (t, 6.9)
133.3
134.1
127.3
30.3
5.77 (t,7.0)
2.33 (m)
2.49 (m)
3.50 (m)
127.8 5.59 (t,7.5)
was diluted with water, and then extracted with EtOAc. The water
portion was subjected to column chromatography (CC) over polyamide
by elution with water and EtOH-water (1:1, v/v). Then the water eluant
was subjected to CC over D101 macroporous adsorption resin by elution
with water and EtOH-water (30%, 60%, and 95%, v/v, successively)
given fractions A1-A4. Fraction A3 (338.5 g) with similar weight dia-
tomite was in sequence to reflux with EtOAc, EtOH, and MeOH (frac-
tion B1, B2 and B3, respectively). Fraction B2 (151.38 g) was subjected
a
b
0
31.4
2.33 (m)
2.55 (m)
3.49 (dd,
30.6
90.6
2.38 (m)
2.58 (m)
3.60 (dd, 8.1,
3.8)
90.4
88.3
8
.2, 3.6)
1
1
1
1
1
1
2
3
4
5
6
1
2
3
4
5
′
′
′
′
′
74.7
26.3
24.5
12.9
27.1
74.7
24.5
26.4
20.9
27.2
73.6
26.4
25
20.9
27.2
104.1
75.3
78.1
71.6
77.9
1.21 (s)
1.23 (s)
1.75 (s)
1.25 (s)
4.37 (d,7.8)
3.26 (m)
3.35 (m)
3.34 (m)
3.27 (m)
1.23 (s)
1.21 (s)
1.83 (s)
1.26 (s)
1.2 (s)
1.22 (s)
1.83 (s)
1.26 (s)
to CC over 200–300 mesh silica gel with CHCl
to acquisition fractions C1 - C7. Then fraction C6 (4.373 g) was sub-
jected to an C18 column with CH OH-water (20%–70%), and finally
purified by preparative HPLC (detected at 230 nm, 8 mL/min) to give 1
12 mg, CH CN-H O, 20:80, v/v, t : 82 min), 2 (8 mg, CH CN-H O,
0:80, v/v, t :86 min), 3 (8 mg, CH CN-H O, 20:80, v/v, t : 78 min),
and 4 (3 mg, CH OH-H O, 40:60, v/v, t : 92 min).
3
-MeOH (15: 1–1: 1, v/v)
106.4 4.45 (d,7.8)
106.4 4.37 (d,7.7)
75.9
78.3
71.6
77.8
3.25 (m)
3.36 (m)
3.33 (m)
3.28 (m)
3.73 (m),
75.9
78.3
71.6
77.8
62.9
3.25 (m)
3.36 (m)
3.33 (m)
3.28 (m)
3.67 (m), 3.87 62.6
(m)
3
(
3
2
R
3
2
′
3.72 (m), 3.87 (m) 62.8
2
R
3
2
R
3
.88 (m)
3
2
R
δ in ppm; J in Hz within parentheses; Measured at 500 MHz for 1H NMR and
25 MHz for C NMR in CD
1
3
1
3
OD.
3.4. Enzymatic hydrolysis of 1, 2 and 3
(
60–100 mesh) were from Qingdao Marine chemical company, Jiangsu
Enzymatic hydrolysis of 1, 2 and 3 followed the literature [16] with
snailase: compounds 1, 2 and 3 (8.2, 5.6 and 5.3 mg, respectively),
dissolved in H O (1.0 mL) with snailase (10.0, 8.0 and 8.0 mg, respec-
tively), was stirred at 37 °C for 8 h. After the reaction and cooling, the
mixture was extracted with EtOAc. The water layer was subjected to CC
Changfeng chemical company, D101 macroporous purchased from the
Tian jin Huang hua chemical Co.LTD and need the ODS (50 μm, Tokyo,
Japan). Thin layer chromatography was performed on glass coated si-
lica gel GF254. The spots can be seen under UV light, or 10% of sulfuric
acid sprayed in EtOH and then heated.
2
3 2
on silica gel (300–400 mesh) with CH CN-H O (8:1, v/v) to afford
189

L. Ni et al.
Fitoterapia 128 (2018) 187–191
Fig. 5. The CD curve of Triptergosidols A-D (1-4).
Table 3
3.5. Determination of absolute configuration of the 10,11-diol unit in 1
1
H and 13C NMR spectrosopic data assignments for 2a and 3a.
Snatzke's method was used to consider the absolute configuration of
the C-10 in 1. The detailed operation instructions were the same as
published procedure [13].
NO.
2a
3a
1
1
2
3
4
5
6
7
8
9
9
1
1
1
1
1
1
a
b
5.04 (dd,10.8,1.5)
5.20 (dd,17.4,1.5)
5.95 (dd,17.4,10.8)
112.0
5.04 (dd,10.8,1.5)
5.21 (dd,17.4,1.5)
5.96 (dd,17.4,10.8)
112.1
146.4
73.7
47.0
123.4
139.2
135.1
129.8
31.3
146.4
73.8
47.3
126.7
131.5
134.2
127.8
30.4
3.6. Isolated new compounds
2.33 (m)
5.61 (td,15.6,7.0)
6.13 (d,15.6)
2.36 (m)
5.73 (dt,15.6,7.5)
6.51 (d,15.6)
3.6.1. Triptergosidol A (1)
25
Colorless oil; [α]
D
3 3
−233.6 (c 0.1 CH OH); UV (CH OH) λmax (log
ε) 200.8 (2.77) nm, 235.6 (2.92); IR (microscope) νmax 3380, 2974,
5.56 (t,7.1)
2.16 (m)
2.49 (m)
5.45 (t,7.2)
2.23 (m)
2.54 (m)
−
1
1
645, 1374, 1079, 1041, 970, 924, and 641 cm ; CD (CH
3
OH) λmax
, 500 MHz) and
4
C NMR (methanol-d , 125 MHz), see Table 1; HRESIMS m/z 439.2316
a
b
0
1
2
3
4
5
1
(Δε) 200 (+3.10), 230 (+3.56); H NMR (methanol-d
4
13
3.34 (overlap)
79.8
73.9
24.8
25.9
12.9
27.1
3.33 (overlap)
79.9
73.9
24.8
25.9
21.0
27.2
M + Na]+ (calcd for C21
36NaO , 439.2302).
[
H
8
1.18 (s)
1.21 (s)
1.76 (s)
1.24 (s)
1.18 (s)
1.25 (s)
1.84 (s)
1.25 (s)
3.6.2. Triptergosidol B (2)
2
5
Colorless oil;[α]
D
3 3
−150.4 (c 0.1 CH OH); UV (CH OH) λmax (log
ε) 200.8 (2.49) nm, 239.0 (2.68); IR (microscope) νmax 3381, 2975,
δ in ppm; J in Hz within parentheses; Measured at 600 MHz for 1H NMR and
50 MHz for C NMR in CD
−1
1
(
645, 1374, 1076, 1036, 970, 923, and 631 cm ; CD (CH
3
OH) λmax
, 500 MHz)
, 125 MHz), see Table 2; HRESIMS m/
z439.2314 [M + Na] (calcd for C21 36NaO , 439.2302).
1
3
1
3
OD.
1
Δε) 200 (+1.48), 214.5 (−1.10); H NMR (methanol-d
4
13
and C NMR (methanol-d
4
glucose (1.8 mg). The EtOAc layer was purified by HPLC (30% CH
O, v/v, t : 78 min, detected at 230 nm, 8 mL/min) to acquired 1a
3.3 mg), 2a (1.2 mg) and 3a (1.0 mg).
3
CN-
+
H
8
H
(
2
R
3
.6.3. Triptergosidol C (3)
25
Colorless oil;[α]
D
3 3
−183.6 (c 0.1 CH OH); UV (CH OH) λmax (log
190

L. Ni et al.
Fitoterapia 128 (2018) 187–191
ε) 200.8 (2.84) nm, 235.6 (3.12); IR (microscope) νmax 3362, 2973,
Acknowledgement
−
1
1
646, 1378, 1078, 1033, 967, 923, and 632 cm ; CD (CH
3
OH) λmax
, 500 MHz) and
, 125 MHz), see Table 2; HRESIMS m/z439.2316
M + Na] (calcd for C21 36NaO , 439.2302).
1
(
Δε) 200 (+1.10), 242 (−0.60); H NMR (methanol-d
4
This work was supported by National Natural Science Foundation of
China (No. 21572275), CAMS Innovation Fund for Medical Sciences
(No. 2016-I2M-2-003), and the Educational and scientific research
program for young and middle-age instructor of Fujian province (NO.
JAT160173).
1
3
C NMR (methanol-d
4
+
[
H
8
3
.6.4. Triptergosidol D (4)
2
5
Colorless oil; [α]
D
3 3
−189.0 (c 0.1. CH OH); UV (CH OH) λmax (log
ε) 200.8 (2.43) nm, 235.2 (2.85); IR (microscope) νmax 3370, 2972,
Appendix A. Supplementary data
−
1
1
644, 1377, 1077, 1035, 967, 922, and 637 cm ; CD (CH
3
OH) λmax
, 500 MHz)
, 125 MHz), see Table 2; HRESIMS m/
z439.2306 [M + Na] (calcd for C21 36NaO , 439.2302).
1
(
Δε) 200 (+0.80), 240.5 (+1.01); H NMR (methanol-d
4
Copies of spectra of compounds 1-4 and 1a-3a. Supplementary data
to this article can be found online at https://doi.org/10.1016/j.fitote.
2018.05.018.
1
3
and C NMR (methanol-d
4
+
H
8
3
.6.5. Triptergerol A
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4
,
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3
OH) λmax (Δε) 317.5 (+ 0.11), 406.5
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The present investigation reported the isolation of four compounds
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[
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[
5
8.2 ± 5.6% at concentration 60 μM, respectively.
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Conflict of interest
3
0046–30052.
[
21] X.-K. Zheng, J.-H. Guo, W.-S. Feng, H.-W. Li, Three new sesquiterpenes from
The authors declare no compete in financial interests.
Euonymus schensianus maxim, Chin. Chem. Lett. 20 (2009) 952–954.
191