全 文 ：橙黄网孢盘菌中的新没药烷倍半萜?
张 凌1 , 2 , 王 飞1 , 3 , 董泽军1 , 刘吉开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; 3 云南西力生物技术有限公司 , 云南 昆明 650204 )
摘要 : 从橙黄网孢盘菌 ( Aleuria aurantia) 中分离得到一个新的没药烷型倍半萜 , 其化学结构通过波谱方法
鉴定为 : (1 R, 7 S )-15-hydroxy-1- epi-β-bisabolol , 命名为 aleuriol (1)。没药烷型倍半萜在盘菌科中为首次报道。
关键词 : 橙黄网孢盘菌 ; 没药烷倍半萜 ; Aleuriol
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2008) 05 - 611 - 03
New Bisabolane Sesquiterpene from Culture Broth of the
Fungus Aleuria aurantia (Pezizaceae)
ZHANG Ling1 , 2 , WANG Fei1 , 3 , DONG Ze-Jun1 , LIU J i-Kai1 * *
( 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; 3 BioBioPha Co ., Ltd ., Kunming 650204 , China)
Abstract: A new bisabolane-type sesquiterpene: (1 R, 7 S ) -15-hydroxy-1-epi-β-bisabolol , named aleuriol (1) was iso-
lated from culture broth of the fungus Aleuria aurantia (Pezizaceae) . The structureof 1 was elucidatedon the basis of ex-
tensive spectroscopic analysis . This is thefirst example of bisabolane isolated from the family .
Key words: Aleuria aurantia; Bisabolane sesquiterpene; Aleuriol
Aleuria aurantia of the family Pezizaceae is a
widespread ascomycete and easily recognized by the
sizableorange cups fromdisturbed ground . Thisorange
peel fungus grows onbare clay or disturbed soil , which
fruitsmainly in late summer and autumn . Thechemical
investigation of A. aurantia began in 1938 , and then a
series of carotenoids were isolated from this fungus
( Lederer, 1938; Valadon, 1964; Liaaen-Jensen,
1965; Arpin et al. , 1973) . One of our efforts to dis-
cover bioactive substances from higher fungi in South-
western China ( Liu, 2005 , 2006; Zhang et al. ,
2006; Yang et al. , 2007 ) has led to the isolation of a
new sesquiterpene named aleuriol (1) from the culture
broth of A. aurantia . This is the first representative of
bisabolane sesquiterpene in the family . Herein, details
of the isolation and structure elucidation of aleuriol (1)
aredescribed .
Results and discussion
Compound 1, obtained as colorless needles, has a
molecular formulaof C15 H26O2 basedonHRESI-MS (pos .) ,
showing a quasi-molecular ion at m?z 261 .1835 ( cal-
cd . for C15 H26 O2 Na, 261 .1830 ) , requiring three de-
grees of unsaturation . The IR spectrum displayed ab-
sorption bands of hydroxyl ( 3260 cm- 1 ) and double
bond ( 3029 , 1638 cm- 1 ) groups . The 13 C NMR
云 南 植 物 研 究 2008 , 30 (5) : 611～613
Acta Botanica Yunnanica DOI : 10 .3724?SP. J . 1143 .2008.07347
?
?? ?Author for correspondence; Tel : + 86 - 871 - 5216327 ; E-mail : jkliu@ mail .kib. ac. cn
Received date: 2008 - 01 - 21 , Accepted date: 2008 - 05 - 06
作者简介 : 张凌 ( 1982 - ) 女 , 在读硕士研究生 , 从事高等真菌化学研究。 ?
Foundation items: The foundations from Chinese Academy of Sciences ( KSCX1-YW-R-24 ; KSCX2-YW-G-025 )
(DEPT) spectrum (Table 1) exhibited 15 carbon sig-
nals, including a set of double bond at δ137 .1 (s) ,
120 .2 (d) , an oxygen-bearing quaternary carbon atδ
72 .5 (s) , as well as characteristic signals atδ131 .5
(s) , 124 .6 ( d) , 26 .4 ( t) , 25 .7 ( q) , 17 .6 ( q)
contributed to an isopentenyl unit . The above NMR
character allowed us to conclude that compound 1 pos-
sessed a skeleton of sesquiterpene containing only one
alicyclic ring .
Table 1 NMR data for 1 in CDCl3
No . δC δH HMBC
1 ?72 .5 ( s)
2 ?34 .2 ( t) 1 E. 97 ( br d, 16 ?. 0 ) ; C-3 , C-4 , C-6
2 E. 17 ( br d, 16 ?. 0 )
3 ?120 .2 ( d) 5 E. 57 ( br s) C-1 , C-2 , C-5 , C-15
4 ?137 .1 ( s)
5 ?22 .6 ( t) 2 E. 02 ( m) ; 2 . 22 ( m) C-1 , C-3 , C-4 , C-15
6 ?30 .3 ( t) 1 E. 59 - 1 ?. 65 ( m) C-2 , C-4 , C-7
7 ?42 .1 ( d) 1 E. 44 ( m) C-1 , C-2 , C-14
8 ?30 .8 ( t) 1 E. 05 ( m) ; 1 . 58 ( m) C-1 , C-10 , C-14
9 ?26 .4 ( t) 1 E. 88 ( m) ; 2 . 08 ( m) C-7 , C-10 , C-11
10 ?124 .6 ( d) 5 E. 08 ( br t, 7 . 1) C-8 , C-12 , C-13
11 ?131 .5 ( s)
12 ?25 .7 ( q) 1 E. 67 (s) C-10 , C-11 , C-13
13 ?17 .7 ( q) 1 E. 59 (s) C-10 , C-11 , C-12
14 ?13 .5 ( q) 0 E. 94 ( d, 6 . 8 ) C-1 , C-7 , C-8
15 ?66 .9 ( t) 3 E. 99 (s) C-3 , C-4 , C-5
The NMR spectra were similar to those of ( 1 S,
7 S )-β-bisabolol ( 2c ) ( Fráter and Müller, 1989 ) ,
and theobvious NMR differences were as follows: Me-
15 signals at δC 23 .3 ( q) , δH 1 .69 (3H , s) of 2c
were absent and replaced by newly arising down-field
resonances atδC 66 .9 ( t) , δH 3 .99 ( 2H, s) in 1 ,
indicating that the methyl must be substituted by a
hydroxyl group in 1 . This conclusion was further sup-
ported by the fact that the following significant HMBC
correlations (Table 1 ) were observed: from H - 3 to C
- 1 , C - 5 , C - 15 ; fromH - 15 to C - 3 , C - 5 . There-
fore, the gross structure of 1 was elucidated as 15-
hydroxy-β-bisabolol , shown in Fig . 1 , named aleuri-
ol .The absolute configuration of 1 was deduced to be
(1 R, 7 S) by comparison of its optical rotation value
with those of reported analogues of β-bisabolol ( Table
2) ( Ohloff et al. , 1986; Kim et al. , 2005) . Conse-
quently, the ultimate structure of 1 was established to
be ( 1 R, 7 S )-15-hydroxy-1- epi-β-bisabolol .
Fig . 1 Structures of compounds 1 and 2a-2d
Table 2 The optical rotation values of 1 and its analogues
Compound Configuration Value Solvent
1 ?1 R , 7 S - 48 M. 7 c 0 .20 , CHCl3
2 ?a 1 R , 7 S
- 57 M* c 0 .1 , CHCl3
2 ?b 1 S, 7 R + 49 \* c 0 .49 , CHCl3
2 ?c 1 S, 7 S + 7 7. 2 * c 0 .28 , CHCl3
2 ?d 1 R , 7 R - 5 (. 2 ** c 1 .0 , CHCl3
*?** ?These data were cited from Ohloff et al. , 1986 and Kim et al. ,
2005 , respectively
Experimental
General Optical rotation was measured on a Horiba SE-
PA-300 polarimeter . IR spectrum was obtained with a Bruker
Tensor 27 FT-IR spectrometer with KBr pellets . NMR spectra
were recorded with a Bruker DRX-500 spectrometer in CDCl3
(δH = 7 .26 ppm, δC = 77.00 ppm) at roomtemperature . EIMS
was taken on a Finnigan-MAT 90 instrument and HRESIMS
recorded with API QSTAR Pulsar i spectrometer . Silica gel (200
- 300 mesh) andLiChroprep RP-18 silicagel ( 40 - 63μm, Mer-
ck, Dramstadt, Germany) were used for column chromatogra-
phy . Fractionsweremonitored by TLC and spots were visualized
by heatingsilicagel plates immersed withvanillin-H2 SO4 in etha-
nol .
Fungal material and fermentation The fresh fruiting
bodies of A. aurantia were collected at the southern part of Gaol-
igongMountains in Yunnan Province, China, in July 2007 and
identified by Prof . ZANGMu . Thevoucher specimen was depos-
ited at the Herbarium of Kunming Institute of Botany, Chinese
Academy of Sciences . The culture medium consisted of potato
(peel off) 200 g, glucose 20 g, KH2 PO4 3 g, MgSO4 1 .5 g, cit-
ric acid0 .1 gandthiamin hydrochloride10 mgin1 L of sterilized
water . Reagent bottleswere used as flask (size: 500 ml ; volume
of media: 380 ml ) . The pH valuewasadjustedto6 .5 beforeau-
toclaving . Fermentation was carried out on a shaker at 22℃ and
140 r?min for 26 days .
Extraction and isolation The culture broth ( 22 L ) was
216 云 南 植 物 研 究 30 卷
extracted by EtOAc for three times . The EtOAc extract (6 . 2 g)
was applied on a silica gel column, which eluted stepwise with
petroleum ether?acetone solvent system . Fraction 3 ( 220 mg)
from petroleum ether?acetone (10∶1 , v?v) was repeatedly isolat-
ed by silicagel to get atarget portion (40 .6 mg) mainly contain-
ing 1 , whichwas further purified by RP-18 column (90% MeOH
in H2 O) to afford aleuriol (1 ; 26 .8 mg) .
Aleuriol (1 , 1 R, 7 S-15-hydroxy-1- epi-β-bisabolol ) : col-
orless needles . [α] 26D = - 48 .7 ( c 0 .20 , CHCl3 ) . IR (KBr) :
ν= 3260 , 3029 , 1638 , 1375 , 1073 , 890 cm- 1 . 1 H- and 13 C-
NMR: seeTable1 . EIMS: m?z ( % ) = 220 ( 30 ) [M-H2 O] + ,
189 (15) , 177 ( 16) , 138 ( 43) , 123 ( 30 ) , 109 (68 ) , 107
(60) , 96 (48) , 82 (100) . HRESIMS ( pos .) : 261 .1835 ( cal-
cd . for C15 H26 O2 Na, 261 .1830) .
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3165 期 ZHANG Ling et al . : New Bisabolane Sesquiterpene from Culture Broth of the Fungus Aleuria . . .