全 文 ：伯氏圆孢多孔菌发酵液化学成分?
邵红军1 , 3 , 董泽军1 , 万传星2 , 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 塔里木大学 新疆生产建设兵团塔里木盆地生物资源保护利用重点实验室 , 新疆 阿拉尔 843300 ;
3 中国科学院研究生院 , 北京 100049 )
摘要 : 从担子菌伯氏圆孢多孔菌 ( Bondarzewia berkeleyi ) 发酵液中分离得 4 个苯并呋喃类化合物 (1～4 ) ,
其中一个为新化合物 , 其化学结构通过波谱学方法鉴定为 : ( S )-2- (3′-hydroxyisoprop-1′-enyl ) -2 , 3-dihydro-
benzofuran-5-carbaldehyde (1)。这 4 个化合物均首次从圆孢地花属真菌中分离得到。
关键词 : 伯氏圆孢多孔菌 ; 苯并呋喃 ; 担子菌
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2007) 04 - 483 - 03
Dihydrobenzofurans from Culture Broth of the Basidiomycete
Bondarzewia berkeleyi (Bondarzewiace)
SHAO Hong-Jun1 , 3 , DONG Ze-Jun1 , WAN Chuan-Xing2 , LIU Ji-Kai1 **
(1 State KeyLaboratory of Phytochemistry and Plant Resources in West China, Kunming Instituteof Botany, Chinese Academy
of Sciences, Kunming 650204 , China; 2 Xinjiang Production & Constucion Corps Key Laboratory of Protection
and Utilization of Biological Resources in Tarim Basin, TarimUniversity, Alaer 843300 , China;
3 GraduateSchool of the Chinese Academy of Sciences, Beijing 100049 , China)
Abstract: A new dihydrobenzofuran, ( S )-2-(3′-hydroxyisoprop-1′-enyl )-2 , 3-dihydrobenzofuran-5-carbaldehyde ( 1) was
isolated fromthe culture broth of Bondarzewia berkeleyi together with two known dihydrobenzofurans (2 - 3) and one known
benzofuran (4) . Their structureswereelucidated on thebasis of spectroscopic analysis including2D NMR experiments, and
they were isolated for the first time from thefungi of thegenus Bondarzewia .
Key words: Bondarzewia berkeleyi ; Benzofuran; Basidiomycete
Bondarzewia berkeleyi of thefamily Bondarzewiace
(Basidiomycota) grows at the bases or roots of hard-
wood and deciduous trees of the family Fagaceae ( Dai
et al . 2005 ) . There are no reports on its chemical
constituents in literatures . Bernd and co-workers re-
ported a cytotoxic metabolite, montadial A , isolated
fromthe polypore B. montana ( Bernd et al . 1999 ) ,
they pointed that treatment of these mycelial roots with
aqueous KOH causes an intense yellow color . Taxo-
nomically the genus Bondarzewia has been placed in
theorder Russulales, which is supported by theoccur-
rence of stearoyl-velutinal , the chemotaxonomic marker
compound for this order (Bernd et al . 1999) .
In a continuation of our research for biologically
active substances fromhigher fungi (Ding et al . 2001;
Hellwig et al . 2003; Liu, 2002 , 2005 , 2006; Shao
et al . 2005; Wang et al . 2006) , the brothof B. ber-
keleyi was investigated . In this report, we described
the isolation and structureelucidationof a new dihydro-
benzofuran, ( S ) -2-( 3′-hydroxyisoprop-1′-enyl )-2 ,
云 南 植 物 研 究 2007 , 29 (4) : 483～485
Acta Botanica Yunnanica

?
?? ?Corresponding author; Tel : + 86 - 871 - 5216327; E-mail : jkliu@ mail .kib. ac. cn
Received date: 2007 - 01 - 31 , Accepted date: 2007 - 03 - 16
作者简介 : 邵红军 (1977 - ) 男 , 博士研究生 , 主要从事高等真菌化学和活性研究。 ?
Foundation item: National Natural Science Foundation of China ( 30470027 and 30225048 ) , Foundation of Xinjiang Production & Constuction
Corps Key Laboratory of Protection and Utilization of Biological Resources in Tarim Basin ( BR0610) .
3-dihydrobenzo-furan-5-carbaldehyde ( 1 ) , along with
two known closely related dihydrobenzofurans, ( S ) -
fomannoxin ( 2) , ( + )-5-formyl-2 -(1′, 2′-dihydroxy-
isopropyl ) -2 , 3-dihydrobenzofuran ( 3 ) , and one
known benzofuran, 5-formyl-2 - ( isopropyl-1′-ol )
benzofuran (4 ) (Fig . 1) .
Fig . 1 Structures of compounds 1 - 4
Results and Discussion
Compound 1 wasobtained as light yellowoil , and
assigned themolecular formula C12 H12 O3 based on EI-
MS ( m?z204 , [M] + ) and HR-TOF-MS ( [M + H] +
at m?z205 .0860; calcd . 205 .0864) . Its IR spectrum
revealed the presence of a hydroxyl group ( 3 441
cm- 1 ) and an aldehyde group (2 854 , 2 746 cm- 1 ) .
The 1 H and 13 C NMR spectra ( Table 1 ) exhibited an
aldehyde signal [δH 9 .84 ( s) ; δC 190 .6 ( d, C =
O) ] , aromatic signals [δH 7 .73 ( d, J = 1 .3 , H - 4) ,
7 . 69 ( dd, J = 8 .2 , 1 .3 , H - 6) , 6 . 91 ( d, J = 8 .2 ,
H - 7) ; δC 164 .8 ( s, C - 7a) , 133 .1 ( d, C - 6 ) ,
130 .8 (s, C - 5 ) , 128 .0 (s, C - 4a) , 125 .9 ( d, C
- 4 ) , 109 .7 ( d, C - 7) ] appeared as a 1 , 2, 4-trisub-
stituented benzene ring, terminal disubstituted olefinic
signals [δH 5 .29 (s, H - 2′a) , 5 . 28 (s, H - 2′b) ; δC
146 .8 ( s, C - 1′) , 112 .9 ( t, C - 2′) ] , a methane
signal [δH 5 .46 ( t, J = 8 .9 , H - 2 ) ; δC 84 .9 ( t, C
- 2) ] , a methyoxyl signal [δH 4 .29 ( d, J = 13 .7 , H
- 3′a) , 4 . 25 ( d, J = 13 .7 , H - 3′b) ; δC 63 .0 ( t, C
- 3′) ] , a methylene signal [δH 3 .47 (dd, J = 15 .8 ,
9 .6 , H - 3a) , 3 .21 ( dd, J = 15 .8 , 8.2 , H - 3b) ,
δC 34 .3 ( t, C - 3 ) ] . The cross-peaks between H - 2
and H - 3 , H - 6 and H - 7 in the1 H , 1 H-COSY spec-
tra were also shown . These data suggested that com-
pound 1 has a dihydrobenzofuran framework similar to
the known compound ( S )-fomannoxin ( 2) . Compari-
sons of the spectroscopic data of 1 with those of 2
showed that they were strikingly similar except that a
methyl (δC 17 .1) in 2 was replaced by a hydroxymethyl
atδC 63 .0 in 1 which corroborated by an IR band at 3
441 cm- 1 , and implied that 1 was the 3′-oxygenated
derivative of 2 . The assignments of 1 were further con-
firmed byanalysisof HMBC correlations (Fig . 2 ) . The
absolute configuration of C - 2 in compound 1 was es-
tablished as Sbycomparisonof theoptical rotationval-
ueof 1 ( [α]27 .9D = + 15.2 ( c0 .048 , CHCl3 ) ) with that
of 2 ( [α]22 . 7D = + 51 ( c 0 .01 , CHCl3 ) ) . Thus, the
Fig . 2 Key HMBC correlations of 1
structure of compound 1 was identified as ( S )-2-( 3′-
hydroxyisoprop-1′-enyl )-2 , 3-dihydrobenzofuran-5-car-
baldehyde .
Comparison of the physical and spectroscopic data
with the reported data allowed for the identification of
compounds 2 , 3 , and 4 , obtained fromthe above fun-
gus, as ( S )-fomannoxin (2 ) ( Hirotani et al . 1977;
Kawase et al . 1980 ) , ( + )-5-formyl-2 - ( 1′, 2′-di-
hydroxyisopropyl ) -2 , 3-dihydrobenzofuran ( 3 ) , and
5-formyl-2 -( isopropyl-1′-ol ) benzofuran ( 4) (Donnel-
ly et al . 1988 ) , respectively . It is noted that the di-
hydrobenzofuran derivative possessing S congfiguration
was only found in fungus (Kawase et al . 1980 ) .
Experimental
General experimental procedures Column chromatogra-
phy ( CC) : silica gel ( 200 - 300 mesh, Qingdao Marine Chemi-
cal Inc, Qingdao . P . R . China) , reversed-phase C18 silica gel
(Merk) , and Sephadex LH-20 (Amersham Biosciences) . Frac-
tions weremonitoredby TLC and spotswerevisualized by heating
silica gel plates sprayed with 10 % H2 SO4 in EtOH . Melting
point ( uncorrected) was determinedonan XRC-1 apparatus . UV
spectra were recorded on a Shimadzu UV-2401PC spectropho-
tometer . Optical rotations were measured on a Horiba SEPA-300
spectropolarimeter . IR spectra were obtained with a Tensor 27
spectrometer, with KBr pellets . 1D and 2D NMR spectra were
recorded in Bruker AM-400 and DRX-500 spectrometers . MS
were registered in aVG Autospec-3000 and API QSTAR Pulsar 1
spectrometers; in m?z ( rel . % ) .
Mushroom material and culture The fungus B . ber-
keleyi was collected at the BotanicGarden of Kunming Institute of
Botany, Chinese Academy of Sciences, P . R . China, in July
2003 , and identified by Prof . Zhu-Liang Yang, Kunming Insti-
tute of Botany . The voucher specimen was deposited in the Her-
bariumof Kunming Institute of Botany, Chinese Academyof Sci-
484 云 南 植 物 研 究 29 卷
ences . Culture medium: potato ( peeled) 200 g, glucose 20 g,
KH2 PO4 3 g, MgSO4 1 .5 g, citric acid 0 .1 g and thiamin hydro-
chloride 10 mgin1 l of deionized H2 O ( pH 6 .5 before autoclav-
ing) . The culture liquid was fermented at 25℃ for 20 days on a
rotary shaker (150 rpm) .
Extraction and Isolation The culture broth (12 liter) was
filtered and then successively extracted with AcOEt . The AcOEt
extract was evaporated in vacuo and the oily residue (3. 0 g) was
subjected toCC (RP-18 , MeOH?H2 O (9∶1→1∶1) ) . Thefraction
(0 .3 g) fromMeOH?H2 O (1∶1) was further purified by CC (sili-
ca gel , petroleumether?Me2 CO 12∶1) , and preparativeTLC ( pe-
troleumether?Me2 CO 9∶1 , Rf 0 .20) to afford the pure compound
1 (3 mg) , and preparativeTLC (CHCl3?Me2 CO 30∶1 , Rf 0.30)
togive compound 4 (5 mg) . The fraction ( 0. 7 g) eluted with
MeOH?H2 O (7∶3) was further purified by CC (silica gel , petro-
leumether?AcOEt 15∶1) , and preparativeTLC ( petroleum ether?
AcOEt 10∶1 , Rf 0.23) to give the pure compound 2 (13 mg) .
The fraction (0 .3 g) fromMeOH?H2 O (3∶7) was further isolated
byCC (silicagel , petroleumether?Me2 CO 4∶1) , repeated Sepha-
dex LH-20 ( CHCl3?MeOH 1∶1 ) , and preparative TLC (CHCl3?
MeOH 20∶1 , Rf 0.3) to afford the purecompound3 (4 mg) .
Compound 1 , C12 H12 O3 , light yellow oil ; [α]27 .9D = +
15 .2°( c 0.048 , CHCl3 ) ; UV ( CHCl3 ) λmax nm ( logε) : 237
(2 .79 ) , 294 ( 3 .21 ) ; IR νKBrmax cm- 1 : 3441 , 2956 , 2925 ,
2854 , 2746 , 1656 , 1604 , 1462 , 1109 , 950; 1 H and 13 C NMR
data: seeTable= 1; EI-MS: 204 (45 , M+ , C12 H12 O3 + ) , 186
(34 , [M-H2 O] + ) , 173 ( 68 ) , 145 ( 100 ) , 127 ( 40) , 115
(33) , 91 ( 31 ) , 77 (17 ) ; HR-TOF-MS: 205 .0860 ( [M +
H] + , C12 H13 O3 + ; calcd . 205.0864) .
Compound 2 , C12 H12 O2 ; colorless oil ; [α] 22 .7D = + 51°( c
0 .01 , CHCl3 ) ; IR νKBrmax cm- 1 : 3444 , 3080 , 2856 , 2741 ,
1688 , 1606 , 1248 , 1107 , 944; 1 H and13 C NMR data: seeTa-
ble . 1 ; ESI-MS: 189 ( [M + H] + ) .
Table 1 1 H and 13 C NMR Dataof 1 and 2 (CDCl3 , δ in ppm, J in Hz) .
Pos .
1 ?
δC δH
2 4
δC δH
2 ?84 P. 9 ( d) 5 =. 46 ( t, J = 8 .9 ) 87 .2 (d) 5 . 30 (t, J = 8 .8)
3 ?34 X. 3 ( t) 3 =. 47 ( dd, J = 15 M. 8 , 9 . 6) , 33 .7 (t) 3 . 41 (dd, J = 15 . 9 , 9 .7 ) ,
3 =. 21 ( dd, J = 15 M. 8 , 8 . 2) 3 ?. 08 (dd, J = 15 . 8 , 7 .8 )
4 ?125 b. 9 ( d) 7 =. 73 ( d, J = 1 ?. 3) 125 .8 ( d) 7 . 72 (s)
5 ?130 g. 8 ( s) - 130 . 5 (s) -
6 ?133 b. 1 ( d) 7 =. 69 ( dd, J = 8 (. 2 , 1 . 3) 133 .2 ( d) 7 . 68 (d, J = 8 .2 )
7 ?109 b. 7 ( d) 6 =. 91 ( d, J = 8 ?. 2) 109 .5 ( d) 6 . 90 (d, J = 8 .2 )
4 qa 128 g. 0 ( s) - 128 ?. 2 (s) -
7 qa 164 g. 8 ( s) - 165 ?. 2 (s) -
1 u′ 146 g. 8 ( s) - 143 ?. 1 (s) -
2 u′ 112 j. 9 ( t) 5 =. 29 (s) , 5 ?. 28 (s) 112 .8 ( t) 5 . 10 (s) , 4 J. 95 (s)
3 u′ 63 X. 0 ( t) 4 =. 29 ( d, J = 13 (. 7) , 4 ?. 25 (d, J = 13 .7 ) 17 .1 (q) 1 . 77 (s)
CHO 190 b. 6 ( d) 9 =. 84 (s) 190 ?. 7 ( d) 9 . 83 (s)
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