全 文 ：书天然产物研究与开发 Nat Prod Ｒes Dev 2015，27:1131-1133
文章编号:1001-6880(2015)7-1131-03
Ｒeceived:May 20，2014 Accepted:May 7，2015
Foundation Item:National Natural Science Foundation of China(U1132607，
81102346)
* Corresponding author E-mail:fengtao@ mail． kib． ac． cn;jkliu@ mail．
kib． ac． cn
白黄小脆柄菇发酵液中的一个新的血苋烷型倍半萜
李学梅1，2，尹 霞1，3，李正辉1，冯 涛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，昆明 650201;
2云南农业大学，昆明 650201;3 中国科学院大学，北京 100049
摘 要:从白黄小脆柄菇(Psathyrellacandolleana)发酵液提取物的乙酸乙酯层中分离得到一个新的血苋烷型倍
半萜(1)和一个已知的没药烷型倍半萜(2)。通过质谱、核磁等方法确定化合物 1 的结构为 15-hydroxy-drime-
nol。通过文献对照核磁数据确定化合物 2 为 1α-hydroxy-bisabola-2，10-dien-4-one。
关键词:白黄小脆柄菇;倍半萜;结构鉴定
中图分类号:Ｒ284． 2 文献标识码:A DOI:10． 16333 / j． 1001-6880． 2015． 07． 001
A New DrimaneSesquiterpenoid from Cultures of Fungus Psathyrellacandolleana
LI Xue-mei1，2，YIN Xia1，3，LI Zheng-hui1，FENG Tao1* ，LIU Ji-kai1*
1 State Key Laboratory of Phytochemistry and Plant Ｒesources in West China，Kunming Institute
of Botany，Chinese Academy of Sciences，Kunming 650201，China;2Yunnan Agriculture University，Kunming 650201，China;
3University of Chinese Academy of Sciences，Beijing 100049，China
Abstract:A new drimanesesquiterpenoid15-hydroxydrimenol (1) ，together with a known germacranesesquiterpenoid1α-
hydroxy-bisabola-2，10-dien-4-one (2) ，was isolated from cultures of fungus Psathyrellacandolleana． The new compound
1 was elucidated on the basis of extensive spectroscopic methods，while the known compound 2 was identified by compar-
ison of spectroscopic data with those reported in the literature．
Key words:Psathyrellacandolleana;sesquiterpenoids;structural identification
Introduction
Searching for new and bioactive products from higher
fungi has been a long-term job of our group． Ｒecently，
more and more terpenoids，especiallysesquiterpenoids
have been found from both fruiting bodies and their fer-
mentation broths． For instance，trefolane A［1］ and
conosilane A［2］ are two novel sesquiterpenoids from
cultures of Tremellafoliacea andConocybesiliginea，re-
spectively，while irlactins A-D are also four ring-rear-
ranged carbon skeletons from cultures of Irpexlacte-
us［3］． Boledulins A-C were three non-isoprenoidbotry-
anesesquiterpenoids that have been isolated from cul-
tures of basidiomycete Boletus edulis，and boledulin A
showed certain cytotoxicities against five human cancer
cell lines［4］． In addition，a number of toxic triterpenoids
with a raretrioxaspiroketal backbone have been ob-
tained from French mushroom Tricholomaterreum，
which declared another poisonous mushroom (T． terre-
um)in Europe［5］． In this paper，we report a new dri-
manesesquiterpenoid，namely15-hydroxydrimenol (1) ，
along with a knowngermacranesesquiterpenoid1α-hy-
droxy-bisabola-2，10-dien-4-one (2) (Fig． 1) ，from
cultures of fungus Psathyrellacandolleana．
Fig. 1 Chemicalstructures of compounds 1 and 2
Materials and Methods
General experimental procedures
Optical rotations were measured on a Jasco-P-1020 po-
larimeter (Horiba，Kyoto，Japan)． IＲ spectra were ob-
tained by using a Bruker Tensor 27 FT-IＲ spectrometer
(Bruker，Karlsruher，Germany)with KBr pellets． NMＲ
spectra were acquired with instrument of an Avance III
600 (Bruker，Karlsruher，Germany)． HＲ-EI-MS were
measured on a Waters Autospec Premier P776 mass
spectrometer (Waters，Milford，MA，USA)． Preparative
HPLC was performed on an Agilent 1100 series with a
Zorbax SB-C18(5 μm，9． 4 × 150 mm)column (Agi-
lent Technologies，Santa Clara，CA，USA)． Silica gel
(200-300 mesh，Qingdao Marine Chemical Inc．，Qing-
dao，China)，was used for column chromatography．
Fractions were monitored by TLC (Qingdao Marine
Chemical Inc．，Qingdao，China)and spots visualized
by heating silica gel plates immersed in vanillin-H2SO4
in EtOH．
Fungal material and culture
The fungus Psathyrella candolleana(Pers．) Fr． was
collected from Kunming Institute of Botany in Yunnan
Province，People’s Ｒepublic of China，in 2003． The
fungus was identified by Prof． Zhu-Liang Yang at the
Kunming Institute of Botany． A specimen (No．
KIB20030828)was deposited at Kunming Institute of
Botany，Chinese Academy of Sciences．
Extraction and isolation
The culture broth (21 L)was filtered，and the filtrate
was extracted with ethyl acetate (20 L × 3) ，while the
mycelium was extracted three times with CHCl3-MeOH
(1 ∶ 1)． The EtOAc layer together with the mycelium
extract was concentrated under reduced pressure to give
a crude extract (10 g) ，and the latter was applied to a
silica gel column eluted with a gradient of CHCl3 /
MeOH (1 ∶ 0 → 0 ∶ 1)to obtain five fractions (1-5)
(This part has been described in a previous re-
port［6］)． Fraction 2 (800 mg)was subjected to silica
gel eluted with CHCl3 /Me2CO (10 ∶ 1)to give three
subfractions (3a-3c)． Fraction 3c was separated by
semipreparative HPLC (MeCN /H2O，3 ∶ 7 → 4 ∶ 6，15
mins)to give 1 (3 mg)and 2 (1 mg)．
15-Hydroxydrimenol (1)
Colorless oil; ［α］16D + 6． 8 (c2． 1 MeOH);IＲ (KBr)
υmax3423，2924，1630 cm
-1;1H NMＲ (600 MHz)and
13C NMＲ (150 MHz)data (CDCl3) ，see Table 1;HＲ-
EI-MS m / z 238． 1933 (calcd for C15 H26 O2［M］
+，
238． 1933)．
1α-Hydroxy-bisabola-2，10-dien-4-one (2)
Molecular formula C15H20O;colorless oil;-72． 2 (c1． 2，
MeOH) ;1H NMＲ (600 MHz，CDCl3)δ:4． 38 (1H，m，
H-1) ，6． 78 (1H，br d，J = 5． 7 Hz，H-2) ，2． 45 (1H，
m，H-5a) ，2． 45 (1H，m，H-5b) ，1． 79 (1H，m，H-6) ，
1． 67 (1H，m，H-7) ，1． 59 (1H，m，H-8a) ，1． 20 (1H，
m，H-8b) ，2． 05 (1H，m，H-9a) ，1． 95 (1H，m，H-
9b) ，5． 12 (1H，t，J = 7 Hz，H-10) ，1． 69 (3H，s，H-
15) ，1． 67 (2H，s，H-12) ，1． 59 (3H，s，H-13) ，0． 93
(3H，d，J = 6． 3 Hz，H-14) ;13 C NMＲ (150 MHz，
CDCl3)δ:200． 2 (s) ，145． 3 (d) ，136． 0 (s) ，131． 4
(s) ，125． 7 (d) ，64． 5 (d) ，44． 9 (d) ，37． 4 (t) ，
34. 4 (t) ，33． 8 (d) ，25． 9 (q) ，25． 8 (t) ，17． 7 (q) ，
16． 9 (q) ，15． 7 (q)．
Structural identification
Compound 1 was isolated as a colorless oil． Its molecu-
lar formula were established as C15 H26 O2 on the basis
of ion peak at m/z 238． 1993 in HＲ-EI-MS (calcd for
C15H26 O2［M］
+，238． 1933)． IＲ absorption band at
3423 cm-1 indicated the presence of hydroxy group(s)．
In 1H NMＲ spectrum (Table 1) ，three methyls as sin-
glets were readily identified (δH 0． 84，0． 89，and 1. 78，
each 3H)． In addition，two oxygenated methylenescan
also be established (δH 3． 12，3． 38，3． 75，and 3． 87)．
The 13C NMＲ data (Table 1) ，in combination with
HSQC data，identified fifteen carbon resonances corre-
sponding to three methyls，six methylenes (two oxygen-
ated) ，three methines (one olefinic) ，and three quater-
nary carbons． Analysis of these data suggested that 1
was similar to drimenol，a known compound discovered
in 1950s，which suggested that 1 possessed a drimane-
sesquiterpenoid skeleton． The key difference between 1
and drimenol was that one methyl at C-4 was oxygena-
ted into an oxymethylene (δH 3． 12 and 3． 38 each 1H，
d，J = 10． 8 Hz;δC 71． 4，t) ，as supported by HMBC
correlations from δH 3． 12 and 3． 38 to δC 37． 4 (s，C-
4)and 17． 9 (q，C-14) (Fig． 2)． Detailed analysis of
other 2D NMＲ data (HMBC，1H-1H COSY)suggested
that the other parts of 1 were the same to those of drim-
enol (Fig． 2)． In the ＲOESY spectrum，the correlation
between H-15 and Me-13 suggested that Me-15 rather
2311 Nat Prod Ｒes Dev Vol. 27
than Me-14 was oxygenated into an oxymethylene． De-
tailed analysis of 2D NMＲ data suggested that the other
parts of 1 were the same to those of drimenol (Fig． 2)．
Therefore，compound 1 was established as 15-
hydroxydrimenol，as shown in Fig． 1．
Fig. 2 Key 2D NMＲ correlations of 1
Table 1 NMＲ spectroscopic data of compound 1 (CDCl3，
600 MHz，δ in ppm，J in Hz)
No． δH(in Hz) δC
1 1． 98 (br d，13． 0;1． 07 (td，13． 0，3． 9) 39． 4，t
2 1． 60 (m) ;1． 55 (m) 18． 0，t
3 1． 41 (td，13． 0，3． 9) ;1． 33 (m) 35． 4，t
4 37． 4，s
5 1． 49 (br t，8． 1) 43． 1，d
6 1． 89 (m) 23． 8，t
7 5． 52 (br s) 123． 7，d
8 133． 0，s
9 1． 89 (overlapped) 57． 0，d
10 35． 8，s
11 3． 87 (dd，11． 3，3． 1) ;3． 75 (dd，3． 7，4． 4) 60． 8，t
12 1． 78 (s) 22． 0，q
13 0． 89 (s) 15． 5，q
14 0． 84 (s) 17． 9，q
15 3． 38 (d，10． 8) ;3． 12 (d，10． 8) 71． 4，t
Compound 2 was isolated as a colorless oil． Its NMＲ
data were closely related to those of 1-hydroxy-bisabo-
la-2，10-dien-4-one． The optical rotation = -72． 2
(c1. 2，MeOH)suggested that compound 2 should be 1
(-hydroxy-bisabola-2，10-dien-4-one．［6］
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3311Vol. 27 LI Xue-mei，et al:A New DrimaneSesquiterpenoid from Cultures of Fungus Psathyrellacandolleana