全 文 ：光里白中的两个新苷类成分 ?
李明明1 , 2 , 王 扣1 ,2 , 陈宣钦1 , 2 , 彭丽艳1 , 成 晓1 , 赵勤实1
??
(1 中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室 ,
云南 昆明 650204; 2 中国科学院研究生院 , 北京 100049)
摘要 : 从光里白 ( Diplopterygiumlaevissimum) 的 95% 乙醇提取物中分离得到 2 个新的苷类成分 , 经波谱手
段鉴定了其结构 , 命名为 hymenoside X (1) 和 hexanoside A (2)。
关键词 : 里白科 ; 光里白 ; 苷类成分 ; hymenoside X ; hexanoside A
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2009) 06 - 559 - 04
Two New Glycosides from Diplopterygium
laevissimum (Gleicheniaceae )
LI Ming-Ming
1 , 2
, WANG Kou
1 , 2
, CHEN Xuan-Qin
1 , 2
, PENG Li-Yan
1
,
CHENG Xiao1 , ZHAO Qin-Shi1 * *
(1 State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming
Instituteof Botany, Chinese Academy of Sciences, Kunming 650204 , China;
2 GraduateUniversity of Chinese Academy of Sciences, Beijing 100049 , China)
Abstract: Two new glycosides hymenoside X ( 1) and hexanoside A ( 2) , were isolated from the 95% EtOH extract of
Diplopterygiumlaevissimum . Their structureswere determined by extensive spectroscopic analysis .
Key words: Gleicheniaceae; Diplopterygium laevissimum; Glycosides; Hymenoside X ; Hexanoside A
Diplopterygium laevissimum ( Christ) Nakai , be-
longing to the Gleicheniaceae family, is widely distri-
buted in the northwest of Yunnan Province, China
[Kunming Institute of Botany, Chinese Academy of
Sciences, 2006] . Toour knowledge, no phytochemical
investigation on this species has been reported . In our
previous research on Gleicheniaceae family, we have
reported two highly oxygenated phenolic derivatives and
some diterpene glycosides ( Li et al. , 2006 , 2007 ,
2008; Zhang et al. , 2009) . As a continuation of our
systematic research work on the bioactive constituents
fromfern, the aerial parts of D. laevissimumhad been
studied and two new compounds were isolated . We
herein report the isolation and structure elucidation of
compounds 1 - 2 .
Results and Discussion
Compound 1 was obtained as amorphous powder,
and its molecular formula was elucidated as C21 H26 O10
based on the negative HR-ESI-MS ( [M-H] - at m?z
437 .1460; calcd for C21 H25 O10 , 437 .1447) , requiring
ninedegrees of unsaturation . The IR spectrumshowed
the absorption bands for the hydroxyl ( 3 427 cm- 1 )
and carbonyl groups ( 1 708 cm- 1 ) , and the absorp-
云 南 植 物 研 究 2009 , 31 (6) : 559～562
Acta Botanica Yunnanica DOI : 10 .3724?SP. J . 1143 .2009.09115
?
?? ?Author for correspondence; E-mail : qinshizhao@ mail . kib. ac. cn; Tel : + 86 - 871 - 5223058
Received date: 2009 - 06 - 10 , Accepted date: 2009 - 10 - 27
作者简介 : 李明明 (1984 - ) 男 , 在读硕士研究生 , 主要从事蕨类植物化学研究。 ?
Foun ?dation items: Thefoundations from the project ( P-06-04) of State KeyLaboratory of Phytochemistry and Plant Resources in West China, Kun-
ming Instituteof Botany, Chinese Academy of Sciences, and the 973 Program ( No . 2009CB522300 )
tions at 1 605 cm- 1 , 1 515 cm- 1 and 1 447 cm- 1 sug-
gested it might have an aromatic ring group . The
13
C
and DEPT NMR spectra of 1 exhibited the presence of
a glucosemoiety [δC 62 .6 ( t) , 77 .7 ( d) , 71 .8 ( d) ,
75 .9 ( d) , 74 .5 (d) and 100 .5 ( d) ] , a p-coumaroyl
group [δC 166 .6 (s) , 115 .6 (d) , 145 .6 (d) , 127 .0
(s) , 2×130 .9 ( d) , 2×116 .6 ( d) and 160 .5 (s) ] .
The double bond of p-coumaroyl group was suggested
as trans-due to the big coupling constant ( J = 16 .0
Hz ) . Assignment of glucosidic protons system were
achieved by analysisof 1 H-1 H COSY and HSQC expe-
riments . The other six carbon signals including these
characteristic NMR data: one carbonyl (δC 169 .3 ) ,
two methylenes (δC 36 .4 , 36 .0) , two oxygenated me-
thines (δC 71 .1 , 72 .8 ) , and one methyl group (δC
21 .6) , suggested the aglycone might be aα-pyrone
type compound . From 1 H-1 H COSY and HMBC corre-
lations we confirmed the aglyconewas3-hydroxy-5-hex-
anolide . HMBC correlations between the anomeric pro-
ton H - 1′(δH 4 .72 ) of glucopyranosyl unit and C - 3
(δC 71 .1) of the aglycone showed glucopyranosyl unit
was linked to C - 3 , and H - 2′(δH 4 .83) had HMBC
correlations with C - 9″(δC 169 .3 ) showed the p-cou-
maroyl group was linked to C - 2′.
The 1 H and 13 C NMR spectra of the aglycone was
similar to those of ( 3 R, 5 R )-3-(β-D-glucopyranosy-
loxy )-5-hexanolide, whose absolute structurewas estab-
lished by X-ray crystallographic analysis of its p-bromo-
benzoate derivative ( Toyota et al. , 2001 ) . And by
comparison the optical rotation value of 1 with the re-
ported analogue hymenoside U [α]22D = - 29 .0 ( c =
2 .80 , MeOH) ( Toyota et al . , 2002 ) , the absolute
configuration of 1 was deduced to be (3 R, 5 R) . Con-
sequently, the ultimate structureof 1 was elucidated as
showed in Fig . 1 and named as hymenoside X .
Compound 2 , obtained as amorphouspowder, had
a molecular formula of C22 H30 O11 determined by the
negative HR-ESI-MS ( [ M-H] - at m?z 469.1712;
calcd for C22 H29 O11 , 469 .1709) , requiring eight de-
greesof unsaturation . The NMR data also suggested the
exist of one glucose moiety and a ( E ) -p-coumaroyl
group . Compared with compound 1 , compound 2 had
onemoremethoxyl andone less degreeof unsaturation,
it was deduced to be a ringopenedα-pyrone-type com-
pound . HMBC correlations between the methoxyl pro-
tons (δH 3 .52) and C - 1 (δC 172 .0 ) of the aglycon
showed methoxyl unit was linked to C - 1 . Compound 2
related to 1 and might be produced from 1 during the
use of methanol ( Toyota et al. , 2002) . Thus, struc-
tureof 2 was elucidated and named as hexanoside A .
Experimental
General Optical rotation was measured on a Horiba SE-
PA-300 polarimeter . IR spectra was obtained with a Tensor 27
FT-IR spectrometer with KBr pellets . The 1 H and 13 C NMR
spectra were recorded on Bruker AV-400 and DRX-500 spec-
trometers in CD3 COCD3 at room temperature (δ in ppm, J in
Hz) . FAB-MSwas carriedout on aVGAutospec-3000 spectrom-
eter . HR-ESIMS was recorded with an API QSTAR Pulsar i
spectrometer . Silicagel (200 - 300 mesh) , Silicagel H (Qingd-
ao Marine Chemical Ltd ., China) and LiChroprep RP-18 silica
gel (40 - 63μm, Merck, Dramstadt, Germany) were used for
column chromatography . Fractions were monitored by TLC and
spotswere visualized by heating silica gel plates immersed with
15% H2 SO4 in ethanol . Solvents were distilled prior to use .
Fig . 1 The structures of 1 and 2
065 云 南 植 物 研 究 31 卷
Fig . 2 Key 1 H-1 H COSY and HMBC correlations of compounds 1 and 2
Preparative HPLC was performed on a ShimadzuLC-8A prepara-
tive liquid chromatograph with Shimadzu PRC-ODS (K ) column .
Sephadex LH-20 (AmershamPharmacia biotech, Sweden) .
Plant material The aerial parts of Diplopterygiumlaevis-
simum ( Christ) Nakai were collected from Pingbian, Yunnan
Province, China in July 2007 and identified by professor Cheng
Xiao at Kunming Institute of Botany, Chinese Academy of Sci-
ences . A voucher specimen (No . 200707A03) has been depos-
ited in the State Key Laboratory of Phytochemistry and Plant Re-
sources in West China, Kunming Institute of Botany, Chinese
Academy of Sciences .
Extraction and isolation The dried and powdered plant
materials (2 . 6 kg) were extracted with95 % EtOH ( 12 L , each
2 d) for three times . After evaporation of the solvent in vacuo,
theconcentrate was suspended into H2 O and partitioned succes-
sively with EtOAc . The EtOAc extract ( 100 g) was chromato-
graphed on a silica gel column, eluting with CHCl3?MeOH (1∶0
to5∶5) togivefivefractions (Fr . 1—Fr . 5) . Fr . 2 was further
subjected to column chromatographover silica gel ( CHCl3?MeOH
9∶1) and Sephadex LH-20 (MeOH ) , then purified semi-HPLC
(MeOH?H2 O 38∶62) to get 1 (6 mg) and 2 (7 mg) .
hymenoside X (1) : amorphous powder; [α]18.8D = - 42 .1
Table 1 1 H and 13 C NMR data for compounds 1 and 2 in CD3 COCD3 . δ in ppm, J in Hz .
NO ?.
1 ?
δ (C) δ ( H)
2 ?
δ ( C) δ ( H)
1 ?169 4. 3 s 172 .0 s
2 ?36 %. 0 t 2 3. 54 ( dd, 4 ?. 8 , 17 s. 6)
2 3. 62 ( ddd, 1 ?. 6 , 3 s. 2 , 17 K. 6) 40 .5 t
2 +. 45 ( dd, 5 . 2 , 16 k. 0)
2 +. 51 ( dd, 7 . 6 , 16 k. 0)
3 ?71 ?. 1 d 4 3. 34 ( m) 75 . 7 s 4 +. 26 ( t, 8 ^. 0 )
4 ?36 %. 4 t 1 3. 71 ( ddd, 3 ?. 2 , 11 .6 , 14 p. 0)
2 3. 13 ( br d 14 ?. 0) 45 .4 t
1 +. 56 ( dt, 4 . 0 , 14 [. 0 )
1 +. 82 ( dt, 8 . 0 , 14 [. 0 )
5 ?72 ?. 8 d 4 3. 65 ( m) 65 .4 d 3 +. 87 ( m)
6 ?21 ?. 6 q 1 3. 24 ( d, 7 v. 6) 24 .1 q 1 +. 10 ( d, 6 n. 4 )
Glc-1 ?′ 100 /. 5 d 4 3. 72 ( d, 8 v. 0) 101 . 8 d 4 +. 69 ( d, 8 n. 0 )
2 u′ 74 ?. 5 d 4 3. 83 ( t, 8 f. 0 ) 74 .5 d 4 +. 77 ( t, 8 ^. 0 )
3 u′ 75 ?. 9 d 3 3. 65 ( m) 76 .0 d 3 +. 59 ( m)
4 u′ 71 ?. 8 d 3 3. 44 ( m) 71 .9 d 3 +. 39 ( m)
5 u′ 77 ?. 7 d 3 3. 41 ( m) 77 .6 d 3 +. 38 ( m)
6 u′ 62 %. 6 t 3 3. 86 ( m) , 3 ?. 44 ( m) 62 .8 t 3 +. 86 ( m) , 3 . 66 ( m)
1 u″ 127 4. 0 s 126 ?. 9 s
2 3″, 6″ 130 ?. 9 2×d 7 .53 ( d, 8 v. 4) 130 .8 2×d 7 +. 54 ( d, 8 n. 4 )
3 3″, 5″ 116 ?. 6 2×d 6 .92 ( d, 8 v. 4) 116 .7 2×d 6 +. 88 ( d, 8 n. 4 )
4 u″ 160 4. 5 s 160 ?. 6 s
7 u″ 145 /. 6 d 7 3. 60 ( d, 16 ?. 0) 145 . 2 d 7 +. 59 ( d, 16 . 0)
8 u″ 115 /. 6 d 6 3. 31 ( d, 16 ?. 0) 115 . 8 d 6 +. 32 ( d, 16 . 0)
9 u″ 166 4. 6 s 166 ?. 5 s
OCH3 ?51 .7 q 3 +. 52 (s)
1656 期 LI Ming-Ming et al. : Two New Glycosides from Diplopterygiumlaevissimum (Gleicheniaceae)
( c = 0 .11 , MeOH ) ; UV λMeOHmax ( logε) : 313 ( 4 .12 ) , 226
(3 .88) , 211 ( 3 .87 ) , 199 ( 3 .87 ) , 192 ( 3 .86 ) ; IR νKBrmax
cm- 1 : 3426 , 1708 , 1632 , 1605 , 1515 , 1447 , 1384 , 1263 ,
1172 , 1070 cm- 1 ; 1 H and 13 C-NMR: see Table 1; FAB-MS
(neg .) m?z: 437 [M-H ] - ; HR-ESI-MS ( neg .) : 437 .1460
[M-H] - ( C21 H25 O10 ; calcd . 437 .1447) .
hexanoside A (2 ) : amorphous powder; [α]19.1D = - 38 .5
( c = 0 .10 , MeOH ) ; UV λMeOHmax ( logε) : 314 ( 3 .95 ) , 227
(3 .70) , 211 ( 3 .69 ) , 200 ( 3 .70 ) , 194 ( 3 .66 ) ; IR νKBrmax
cm- 1 : 3427 , 2926 , 1716 , 1632 , 1605 , 1515 , 1440 , 1265 ,
1172 , 1075 , 1033 cm- 1 ; 1 H and 13 C NMR: seeTable1 ; FAB-
MS ( neg .) m?z: 469 [ M-H ] - ; HR-ESI-MS ( neg .) :
469 .1712 [M-H] - ( C22 H29 O11 ; calcd . 469 .1709) .
Acknowledgements : The authors aregrateful to the members of
the Analytical Group in State Key Laboratory of Phytochemistry
and Plant Resources in West China, Kunming Institute of Bota-
ny, for the spectral measurements .
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* * * * * * * * * * * * * * *
更 正
发表于本刊 2009 年第 4 期的“《郑万钧专集》书评”, 由于作者和编辑部的疏忽 ,
以下几处需作更正 :
误 正 页码
袭 求 388 y页第 28 行
中国科学院新疆生物土壤沙漠研究所 新疆师范大学 388 y页第 29 行
另外 , 在“子承父业的几例中”还应加入“原中国科学院林业土壤研究所的
刘慎谔和刘?心”。
265 云 南 植 物 研 究 31 卷