This article was downloaded by: [York University Libraries]On: 13 November 2014, At: 07:28Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Journal of Asian Natural ProductsResearchPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/ganp20

Two New Taxane Diterpenoids fromthe Seeds of the Chinese Yew, TaxusyunnanensisQing-Wen Shi a , Takayuki Oritani , Takeyoshi Sugiyama a ,Ryo Murakami a & Teiko Yamada aa Laboratory of Applied Bioorganic Chemistry, Division of LifeSciences, Graduate School of Agricultural Science, TohokuUniversity , 1–1 Tsutsumi-dori Amamiya, Aoba-ku, Sendai,981-8555, JapanPublished online: 04 Oct 2006.

To cite this article: Qing-Wen Shi , Takayuki Oritani , Takeyoshi Sugiyama , Ryo Murakami& Teiko Yamada (1999) Two New Taxane Diterpenoids from the Seeds of the ChineseYew, Taxus yunnanensis , Journal of Asian Natural Products Research, 2:1, 71-79, DOI:10.1080/10286029908039894

To link to this article: http://dx.doi.org/10.1080/10286029908039894

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information(the “Content”) contained in the publications on our platform. However, Taylor& Francis, our agents, and our licensors make no representations or warrantieswhatsoever as to the accuracy, completeness, or suitability for any purpose of theContent. Any opinions and views expressed in this publication are the opinions andviews of the authors, and are not the views of or endorsed by Taylor & Francis. Theaccuracy of the Content should not be relied upon and should be independentlyverified with primary sources of information. Taylor and Francis shall not be liablefor any losses, actions, claims, proceedings, demands, costs, expenses, damages,and other liabilities whatsoever or howsoever caused arising directly or indirectly inconnection with, in relation to or arising out of the use of the Content.

This article may be used for research, teaching, and private study purposes. Anysubstantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,systematic supply, or distribution in any form to anyone is expressly forbidden.

Terms & Conditions of access and use can be found at http://www.tandfonline.com/page/terms-and-conditions

Dow

nloa

ded

by [

Yor

k U

nive

rsity

Lib

rari

es]

at 0

7:28

13

Nov

embe

r 20

14

JA?VFR. Vol. 2. pp. 71 79 Rcprinls available directly fimm the publisher Photocopying permitted by Ixrnse only

,(' 1999 OPA (Ovrrseas Publishers Association) N.V Published by license uiidcr

tlic Harwood Academic Publishers imprmt, part o f ' l hc Gordon and Brrach Puhhshmg Group.

Printed in Malaysla

TWO NEW TAXANE DITERPENOIDS FROM THE SEEDS OF THE CHINESE YEW,

TAXUS YUNNANENSIS

QING-WEN SHT, TAKAYUKI ORITANI*, TAKEYOSHI SUGIYAMA, RYO MURAKAMI

and TEIKO YAMADA

Luborutory of' Applied Bioovganic Chemistry, Division of Life Sciences, Grurhiuce School of Agricultural Scierzcc, Tohoku University,

1-1 Tsutsumi-dori Arriumiyn, Aobu-ku, Sendui 981-8555, Japan

(Rerewed 9 March 1999, Rrvised 21 M a j 1999. In firiuljorm 15 June 1999)

A new taxoid and a taxinine analogue were isolated from the seeds of the Chinese yew, Tuxus yuiznmemix The structures were established as 13a-acetoxy-5cu-(3'-dimethylamino-3'-phenyl)- propionyloxy-l l(15 - l)-abrotaxa-4(20), 1 I-diene-9cu, lO$diol and 2cu-acetoxy-5a-cinnamoyl- o x y - 9 ~ , lO~-dihydroxy-taxa-4(20),1 I-diem- 13-one on the basis of lD, 2D NMR, and MS spectral analysis.

K ~ v ~ v o r d s Taxus ~unnnanensu. Taxaceac, Taxoids, 1 l(1 S - l)-Abrotaxane, Seeds

INTRODUCTION

The genus Taxus comprises about 10 species in the world, five of them are distributed in China and southeastern Asia. Taxus yunnanensis, which was indigenous to China, is an evergreen tall tree or shrub mainly distributed in the wet valley area of Yunnan, Sichuan Provinces, and Tibet Autonomous Region in the south-west of China. Previous studies on taxane diterpenes in the bark, leaves, branches, and root of this plant have resulted in the isola- tion of more than 40 new taxane diterpenoids [l-221. In the course of our studies on the yew tree, we have investigated the constitutions of the leaves, bark, and seeds of Chinese yew, Taxus chinensis var. mairei [23-271. In view

*Corresponding author. Tel./Fax: 081-22-717 8783. E-mail: shi@biocheIn.tohoku.ac.jp

71

Dow

nloa

ded

by [

Yor

k U

nive

rsity

Lib

rari

es]

at 0

7:28

13

Nov

embe

r 20

14

I Y

SCHEME I

of n o report on the constitutions of seeds of T. .1.1/17/1~n('/7.\/.). recentl) we investigated the component of the seeds of this plant. and led lo the isola- tion of two new taxane diterpenoids (Scheme I ) . I n this communication w e dcscribe the isolation and characterization of two compounds

RESULTS .4ND DISCUSSIOK

A mcthanolic extract of the seeds of T. ~ , ~ ~ ~ ? ? ~ ~ ~ / ? ~ ~ / ~ . s i , \ was processed a s descri- bed in the Materials and Methods section to afford two new taxane diterpe- noids ( 1 and 2). Compound 1 was isolaled as a colorless gummy substance in a yield of 0.002% on the dry material. EI-MS produced an ion peak a t 177;: 569 ([MI ). The molecular fortnula of compound 1 , C13114707N. w a s deduced from combined analysis of HR-EI-MS at tq/z 569.3353 ([MI ' )

and "C-NMR spectrum. Intensive absorptions at 3400 and 1730 cni i n the 1K spcclruni implied that 1 possesses hydroxyl and ester groups. respectively. 'The 'H-NMR spcctrum of 1. tabulatcd in Table 1. exhibited the proton signals due to the four methyl groups at h 0.X3. 1.15. 1.29. and I .92 ppiii. which were the characteristic signals of the taxane skeleton. Onc acetyl group resonated at a relatively lower field ( h 2. I5 ppm). which was verified by observation of ' k - N M R signals a t (5 171.03 and 20.97ppm. These signals suggested that 1 had ;I tauane-type skeleton. The con- nectivities of the protons at thc taxane skeleton of 1 wcrc determined by analysis of the 'H-IH COSY spectrum. lnlerprelation of 'H-, "C-NMR and HMBC spectra permitted the positional assignment of functional groups. The 'H-NMR signals at 5 5.07 ( I H . br s). 4.67 ( I H . br s ) and 2.75 ( I H, d , J - 7.70 Hz) are characteristic of a n exocyclic methylene atid C'-3 ring junction proton in a taxa-4(20), 1 I-diene, respectively [28]. Additionally. fhur oxygen-bearing one-proton signals appeared a t lower field. Of them. the signal at 6 3.97 ppm ( I H , d , J = 9.61 Hz). which showed cross-peaks w i t h

Dow

nloa

ded

by [

Yor

k U

nive

rsity

Lib

rari

es]

at 0

7:28

13

Nov

embe

r 20

14

TAXANE DITERPENOIDS FROM TAXUS YUNNANENSIS 73

TABLE I 'H- and "C-NMR spectral data of 1 In CDCI,

Posifion ' H J ' H ' H C O S Y '3C

1 62.29 2a 1.88 m H-3a 28.81

3 2.75 d 7.70 H-20 40.1 I 4 147.71 5 5.22 br s H-6 75.16 6 1.60m H-7 27.43 7 1.38 m H-6 25.03 8 41.26 9 3.97 d 9.61 H- 1 OCY 79.39 10 4.40 br d 9.61 H-9@ 69.41 11 140.82 12 142.03 13 5.51 t 7.14 H-14, 18-CH3 80.07 14a 1.13 m H-14/3 44.07

15 76.50 16 1.29 s H-17 29.71

26.59 11.35

19 0.83 s 17.19 20a 5.07 br s H-20b 111.46 20b 4.67 br s H-20a 13-OAc 2.15 s 20.97, 171.03 1' 170.66 2' 2.88 dd 6.97, 13.74 211. 3' 39.69

3' 3.77 t 8.30 21, 2" 67.13 4' 138.57 5' 7.29 m 128.27 6' 7.29 m 12x.12 7' 1.29 m 127.67 N-CHi 2.17 s 42.45

2b 1.28 m H-201

14/3 2.36 dd 6.47, 13.24 H - 1 4 ~ , 138

17 1.15 s H-16 18 1.92 br s H-I3

2'' 2.66 dd 9.07, 13.74 21, 3'

19-CH3, C-1 1 in the HMBC spectrum, was attributed to H-90. The signal at 6 4.40ppm (lH, br d, J=9.61 Hz), which showed a cross peak with H-9a in the IH-'H COSY experiment, and showed cross-peaks with C-11 and C-12 in the HMBC spectrum, was assigned to H- 1Oa. Large vicinal coupling indi- cated a trans-oriented configuration of the H-9p and H - l O a . The spin sys- tem derived from 1 8-CH3, H-l3P, H-14a, and H- 140 was readily interpreted. The signal of three protons as a doublet at 6 1.92ppm was assigned to 18-CH3 based on the long-range coupling with H-130; the triplet at S 5.51 ppm (IH, t, J=7.14Hz), was assigned to H-130; the doublet of doub- lets at 2.36ppm and the multiplet at 6 1.13ppm were assigned to the C-14 methylene protons, H-14,0 and H-14a, respectively, based on their geminal coupling and coupling to H-I3P. The signal at 6 5.22ppm ( lH, br s) was

Dow

nloa

ded

by [

Yor

k U

nive

rsity

Lib

rari

es]

at 0

7:28

13

Nov

embe

r 20

14

characteristic signal of H-5,j. All of the proton-bearing carbons were assigned by a n analysis of the HETCOR spectruni. Four os~gen-cc)ntiiining carbons (C-5. C-9. C- 10, and C-13) wcre correlated with their cori-cspondinp proton signal.;. The H- 1 Otr signal showed cross-peaks with the rcsnnancc!, a t (5 140.82 142.03 and 62.29ppn1, which were assigncd for C-l I. ('-12. k i n d

(.- 1 . i-especti\,ely. The C-I 1 and C-I? carhon signalc showed cross -pcak \vi th the H - l 1,-I rcsonancc, indicated that both ( ' - 1 1 and (.-I2 ai-c thrcc bonds apar t from H-14:j. This means t h a t tlie A ring w a s ;1

i n ;in I I ( 15 - I )ahcotaxane structure [?9.30]. The carbon hignal ; i t h 76.50 ppm. assigncd to the liydroxyl-bearing C'- I 5. displayed ii cmsc-peak ivith the C-16 and C 1 7 methyl resoii;inces ;ii (5 1.29 and 1.15ppm. The C'-1 signal ( h 62.20 ppni). apart from H- 1 O ( 1 ~ a l s o h o w c d thrcc-hond coupling with the H-3ci and C-16. C-17 mcthyl signals. Sincc no ci-oss-peak \\:is

observed between C-16. C-17 (methyl) signals and the C - l 1 olcl'inic carbon i n the HMRC' spectrum further supported the I I ( I 5 - I ) r rhco taxanc . shclt- 1i)n for 1 [3 I ] . The presence of a Winterstein acid [( i ' -d imet l iy lami t~~~-~ ' -p l ic - nyl)-propionyloxyl] moiety in 1 w a s suggested froin thc sign;ils a~ b 2. I 7 (6H. x). ?.SX ( I H . dd , J - 13.74. 6 . 9 7 H ~ ) . 2.66 ( 1 H . dd. ./- 13.74.0.07H/). i . ?7 ( I H , t . I-X.30Hz), and 7 .29ppm i n the ' I t - N M R specti-uln. and the sigllais ;It h 170.66. 39.69. 67.1 3. 138.57. 1%.27. 128.12. 127.67. ai?d 42.45 ppn i n the "C-NMR specti-uni. i n good agreement with Iitcratui'c valties [32] . Further s~ippoi-t w;is provided by tlie fragment ions in 111e EI- MS :it 171 1 103 and I34 (base-peaks). which ~vci-e the chai-acteristiu frag- ments of Winterstein acid [33 751. The location ol' the Wintci-stein acid moiety ~ v i i s deduced a t C-5 from the HhlBC spectimi ( t'ig. 1 ). The I-elatiLc stereochemistry of the terpenoid skeleton of 1 wiis determined from chenii- c x l shifts. coupling constants and NOESY experiment. A coupling constant between H-9 and H-10 of J = 9.61 Hz indicated thar the R-ring MYIS Lhc chair boat conformation [29]. The NOESY experiment established thc

Dow

nloa

ded

by [

Yor

k U

nive

rsity

Lib

rari

es]

at 0

7:28

13

Nov

embe

r 20

14

TAXANE DITERPENOIDS FROM 7.4XUS YCINIVANENSIS 75

OAc

FIGURE 2 Kelative stereochemistry of 1. proposed by NOESY experiment (600 MHz).

relative stereochemistry of 1 at all the position, and the results are shown in Fig. 2 . Thus the structure of 1 was determined as 130-acetoxy-5a-(3'-dime- thylamino-3'-pheny1)-propionyloxy- 1 1 (1 5 + 1 )-nbeotaxa-4(20), 1 1 -diene-9a, 1 Obdiol.

Compound 2, which was isolated as a colorless gummy substance, had a molecular ion peak at mjz 522 in its EI-MS (HR-EI-MS, C31H3807); the base peak was at m/z 131 due to the cinnamoyl ion (C9H70), and a peak at mjz 374 arose from the loss of cinnaniic acid (C9HsO2) from M+. The IR spectrum had bands at 3450 (hydroxy), 3050 (aromatic), 1730 (ester), 1710 (conjugated C=O), 1660. 1620 (benzene), and 1625 (olefinic) cm-'. The LJV spectrum had A,,, at 279 nm due to the cinnamate ester group. The 'H- NMR spectrum had well-dispersed signals suggestive of a taxane deriva- tive containing one acetate group and one cinnamatc group. The fact that 18-CH3 was a sharp singlet suggested that C-13 did not have a hydrogen attached, but instead bore a ketone function. In accordance with this, H2-14 displayed a large J,,, = 19.78 Hz. By means of the 'H-'H COSY spectrum, the complete connection network was established for H-14a-H-144-H- lp-H-2$-H-3a-H-20a-H-20b --H-SD H2-6 H-7a. H-3a and H-5p had allylic coupling with H-20a and H-20b. The lower-field chemical shift of H- 2n: indicated an acetoxy group located at C-2. A pair of distinguished doub- lets with a large coupling constant at S 4.89 and 4.19 ppm were attributed to H- 100 and H-9P, respectively, their chemical shifts indicated there are hydroxyl groups attached to C-9 and C-10, i.e. which was 9,10-dideacetyl taxinine. Its 'H-NMR spectrum was closely comparablc with that of taxi- nine with the exception of that H-98 and H-lOa were shifted upfield. The cinnamate group was located at C-50 in accordance with what has been observed in the other taxinine derivatives [28,36-381. Therefore, the

Dow

nloa

ded

by [

Yor

k U

nive

rsity

Lib

rari

es]

at 0

7:28

13

Nov

embe

r 20

14

structure of 2 was elucidated a s 2a-acetoxy-5~~-ciiinainoylosq.-c)tr. 1 O,l-dihy- droxy-taxa-4(20), 1 1 -diene- 13-one. Compound 2 can be formed chemically from taxinine 1391, but this is the first report as a natural product.

EX PERIMEN'I'AL SECTION

General Experirncntal Procedures

Optical rotations were recorded on a Horiba SEP.4-300 digital polarimeter L I V spectrum was run on a Shimadzu UV-1600 spectro-photometer. I R spectra wei-e obtained on a Jasco IR-8 10 instrument. MS were measured on ii Jeol JMS-700 spectrometer using EI modes. ' H- and "C-NM R spectra Lvc're obtained Varian Unity Inova 600 spectrometers operating at 600 M HI f o r ' H . 150 MHz for I3C nucleus, in CDCI? at 20°C. chemical shifts are expressed in parts per million scale relative to that of tetramethylsilane (TMS. f i = 0) a s a n internal standard, and coupling constants are given in H e w . ' H H ETCOR and HMBC cxperimcnts were performed on the same spectrometer, using standard Varian pulse sequences. I H - ' H C'OSY spectrum w-as measured on Varian GEMINI 2000/300 spectrometer a t 300 MHz. Open column chromatography (CC) w a s performed using Merck silica gel 60 (100 200 mesh). Thin layer chromatography (TLC) was carried o u t with the precoated Merck silica gel 60 F154 plates. Preparative TLC were performed using the sanic type o f plates as used for TL.C but with 0.85 nini (dried for 2411 a t room temperature and aclivated for 3 h at 110°C) thick- ness. the spots were detected under UV (254nm) and/or by spraying with I O 0 h sulfuric acid and then heating on a hot plate.

Plant Material

The seeds of T. ,iw/zmemi.\ were collected in C'ongteng county. Y unnan Province, in the south-west of- China. i n October of 1995. The botanical identification was made by Prof. J .H. Wang, School of Pharmaceutical Sci- ence. Hebei Medical University, the People's Republic of China. A voucher specimen has been deposited in our laboratory of Graduate School of Agri- cultural Science, Tohoku University, Japan.

Extraction and Isolation

Air dried seeds (2.1 kg) were crushed and extractcd with liesane three times :it room tempcrature to remove major part of nondesired neutral component

Dow

nloa

ded

by [

Yor

k U

nive

rsity

Lib

rari

es]

at 0

7:28

13

Nov

embe

r 20

14

TAXANE DITERPENOIDS FROM TAXUS YliNNANE!VSIS 71

The residue was extracted three times with methanol (MeOH): the MeOH extracts were condensed to residue (135 g) under reduced pressure. Sub- sequently this residue was diluted with water and was extracted five times with EtOAc (85g). The combined EtOAc layer was further extractcd with 5% HCI. After neutralization, the aqueous layer was extractcd three times with EtOAc. The combined EtOAc extract, upon evaporation, yielded 8.8 g of yellowish syrup, which was subjected to CC, eluted with hexane-ethyl acetate (2: 1, 1 : 1, 1 :2, 1 :4), 12 fractions were obtained, and fraction 3 (900 mg) was further separated by preparative TLC repeatedly with differ- ent developing solvent (CHCI3-MeOH, 100 : 4.5; hexanc-EtOAc, 1 : 2; hexane-acetone 5 : 3), and finally compound 1 (2.5 mg) and 2 (1 mg) were separated.

13cr-Acetox~-Scr-(3‘-dimethylamino-3~-phrn~~l)-propionyEoxy-l f(15 + I ) - abeotaxa-4(20),ll-diene-9~~,10~-diol (1) Gum, [a]:: -27 (~0 .01 , CHC13). IR (film, CHC13) u,~,,: 3400, 2940, 2850, 2850, 2780, 1730, 1650, 1450, 1430, 1365, 1240, 1180, 1020, 750 and 700cmp’; El-MS: mlz (rcl. int.): 569 ([MI+) (19), 509 ([M-AcOH]+) (8), 451 (37); 192 ([HOCOCH2CH(Me2N)Ph]+) (76), 134 ([Me2N=CHPh]+) (loo), 105 (lo), and 43 (9). HR-EI-MS: 569.3353 (calcd. for C33H4707N, 569.3350), The ‘H- and I3C-NMR spectral data see Table I.

2n- Aceto~~~~-5?-~~-cinnamoyloxq:-9a., I0lir-dihy~rox~i-taxa-4 (20) , I 1 -diene- 13- one (2) Colorless gum: [a]: +132 (c 0.01, CHC13); UV (MeOH) A,,, (logc) 279 (4.3)nm; IR (film, CHC13) urnax: 3450, 3050, 2925, 1730, 1710, 1660, 1625, 1620, 1440, 1370, 1310, 1240, 1170, 1030, and 750cm-I; EI-MS m j z (rel. int.): 522 (30) ([MI+), 374 (18) ([M-cinnamic acid]+), 131 (loo), 103 (98) 91 (loo), 77 (65) , and 43 (100). HR-EI-MS: mlz 522.2621 (calcd. for C31H3X07, 522.2615); ’H-NMR (ppm, 300MHz): 5 2.14 (IH, m, H-l), 5.52 ( lH, br d, J=6.32Hz, H-2), 3.36 ( lH, d, J-6.32Hz, H-3), 5.32 (1H. br s, H-5), 1.95 (2H, m, H-6), 1.75 (2H, m, H-7), 4.19 (lH, d, ./=9.6Hz, H-9), 4.89 ( lH, br d, J=9.6Hz, H-lo), 2.42 (IH, br d, J = 19.78Hz, H-l4cr), 2.83 ( lH, dd, J = 19.78, 7.42Hz, H-l4P), 5.32 ( lH, br s, H-20a), 4.84 ( lH, br s,

7.76 (2H, d, .I=.6.87Hz, H-5’,9’), 7.42 (3H. m, H-6/,7/,8’), 1.22 (3H, s, 16-

(3H, s, CH3CO-). I3C-NMR (75MHz, CDC13): 48.82 (C-l), 69.73 (C-2),

H-20b), 6.44 (IH, d, J = 15.93 Hz, H-29, 7.65 (IH, d, J = 15.93 Hz, H-3’),

CH3), 1.71 (3H, S, 17-CH3), 2.12 (3H, S, 18-CH3), 1.10 (3H, S, 19-CH?), 2.16

43.17 (C-3), 142.58 (C-4), 78.74 (C-5), 28.44 (C-6), 26.16 (C-7), 44.41 (C-8), 77.76 (C-9), 73.41 (C-lo), 155.37 (C-1 l), 135.86 (C-12). 200.05 (C-l3), 36.05 (C-14), 37.54 (C-l5), 25.14 (C-16), 37.91 (C-17), 14.06 (C-l8), 17.58 (C-19). 118.08 (C-20), 169.87 (CH3CO-), 166.53 (C-10, 21.30(CH3CO-).

Dow

nloa

ded

by [

Yor

k U

nive

rsity

Lib

rari

es]

at 0

7:28

13

Nov

embe

r 20

14

18 Q.-W. S l l l ( ' I rrl.

.4 ckno wledgmmts

'I'hc authors arc grateful to Mrs. Yuhko Sugiyama for measuring h e N M R spectra. The financial support for the work described liere conics lioni the Ministry of Education. Science, Sports. and Culture o f Japan through ;I

grant-in-aid for scientific rcscarch.

References

[ I ] W.M. Chen. P.J. Zhangand Q.T. Zheng. Acrir flrrrrrii . .Sh. 1991. 20. 747 751. [2] Z.P. Zhang and Z.J. Jia. Pli,~roc/icJnii.rr,.?. 1990. 29. 3673 3675. 1-71 W.M. Chen. 1.Y. Zhou. P.L. %hang and Q.C. Fiin?. C-'/iiii. < ' l i w . l . v / / . IW3. 4. OW 702. [-+I C.. Rao. J.Y. Zliou. W.M. Chcn. Y . Lu iind Q.T. %hcng. C % i / / . (%w!. l , t , / ( . 100.3. 4.

[i] W.M. C'hen. J . Y . Zhou. P.I.. %hiingand Q.C. t a n g . Chin. C'lfiw. l.c.//. 1993. 4. 605 69s. [6] W.M. Chcn. P.L. Zhang. B. Wit and Q.T. Zhcng. C h r i . C h i i . Lcvr. 1901. 2.441 442. 17'1 Q. YLIC. Q.C. Fang. X.T. Liang. C.H. [Ie and X.L. Jing. Plroirr/ :Zlrc/ . 199s. 61. 775 - J T 7 1x1 0. Yuc. Q.C Pang and X.'l'. Liang. f / 1 ~ ~ r o c ~ h r , r l i i s / r : l . 1996. 43. 639 642. ")I Q. Yue. Q.C Fang. X.T. Liang and C.H. Hc. f / r ~ . r o c ~ h ~ , / i i i \ / r : I . 1995. 39. S i l S73

[ I 0 1 W.M. Chen. P.L. Zhangand J.Y. Zhou. A c / r / P/~(rrm. S i j i . 1994. 29. 207 214 [ 1 I ] Z.Y. Chcn. C.W. Gao :ind Y.S. C'hcn. A m Rorunic~r Sin. 1996. -38. 323 327. [I11 X.K. Lio. D.G. Wu and Z.Y. Wang. Kv.rirc, To,i.q/wo 1992. 37. 21Xh- ?l89. 1131 C'. Rao. l . Y Zhou. W.M. Chcn. Y . Lu and Q.T. Zhcng. -Ic/o P/W/JI . Si ir 11P>4. 29.

... 3T-l 351). 1141 W.M. Chcn. P.L. %hang. 1 . Y . Zhou. X. Lici ;!ntl 0 . C ' . I ; ; I I I ~ . : l c / t r f % e ~ r . / i ~ .Si/#. I6)O-+. 29.

7.51 7.57. I 1.51 J . Y . Zhou. P.L. Zhang. W.M. Chcn ; ind 0.C'. Iriing. f / / i ~ r e ) ( ~ / f r , / i i i . ~ / ~ ~ ILJIH. 48.

13x7 1389. l lh] S.Z. Zhong. L X . Hua and J.S. I.'an. J . h:trr. l J i , d . 1996. 59. h03--6(15. 1171 S.X. Zhanz. C.T. LCC. Y. Kiishirada, K. ('hen. I).C. %h;un$ and K.H. 1.w. ./. .vlJi. 1994.

1181 H.J. Zh:ing. I'. Yoshio. M. Takashi. M. Yoshinori. Y. Kenichiro. W. S img. I). M t i ; i n d

1191 H.J. Zhong. T. Yoshio, M. Takashi. M. Yoshinori. Y . Kcnichii-ci. W. Xiang. 0. M i l i i n i l

1201 H.J. %hang. Y . ' lakedaand H.D. Sun. PA!mc,/ic,riri.\.rri. 1095. 39. I I47 1151. 1211 El.1. Zhnne. H.D. Sunand Y. Takcda. Chin. ('lrcvrr. / . ( , I / . 1905. 6. 479 4x2. 621 H.J. Zhang, Q. Mu. W. Xiang. P. Yao, H.D. Sun and Y . T:ikeda. P/~~./f,c./ioili.r.r, 1' lW7 . d4.

12.31 Q.W. Shi. T. Oritani, H. Kiyoki and T. Horiguchi. .Ver/. /'Iw/. Lc//. 1998. 12. h7 7.1 [24] Q.W. Shi. T. Oritani. T. Sugiyama and 11. Kiyota. l'/m~[r .4fed 1909. 64. 76h--7(+1 1251 Q.W. Shi. T. Oritani. T. Sugiyama and H.J. Kiyoto. . \ ' ~ r r . / ' IYJ I / , 1998. 61. 1437 14411. l%] Q.W. Shi. I.. Oritani and T. Sugiyama. P/n. toc , l~ , , i i i .~ tr~ . 1999. 50. 633--636. 1271 0 . W . Shi. T. Oritani. T. Sugiyama. H. Kiyolii iind '1'. Iloriguchi. Hc,rcwic:i?~li,r IIJ1)O. 51.

12x1 Ci. Appendix). In Tlrc C'licwii.sir.r criitl P / i u r . i r i r r i ~ e i k ~ , ~ ~ ~ ( J / 1'ir.vol errit/ i / r l ) c v Y w / i r i ~ r . Fit1

129] K. Fuji. K . Tanaka. H. Li. T. Shingu, '1'. Yokoi. H.D. Sun and T. Taga. Ti~rr.tr/icc/r.ou 101)5.

1301 S. 7hang. C.T. LCC. T. C'he. Y. Kashiwid. I) . Zhc. A. Mcl'hail and K.J. Lcc. < ' / w J ~ J . S ~ X .

1311 ( i . Appcndino. L. Barhoni. P. Gariboldi, E. Boinh;irtlclli. H. C;;ihctt;i ;ind D . J . Vilcrlx:

(193 693.

.. . .

57. 15x0 15x3.

H.1). Sun. / / V / ( ~ W C ~ ~ C / P . Y 1994. -3. 975-980.

1I.D. Sun. Chin. C % m i . 1.(*//. 1994. 5. 957 960

01 I 915.

X41 X50.

Farina. V.. Amsterdam, 1995. Vol. 22, pp. 55 . 1 0 1 .

51. 10 175--ll) 188.

C * / W / # i . C ' O / I 1 / / ~ 1 f / / . 1994. 1561 - 1563.

< 'hC/ l l . ,%fJl'.. ! . / l C / ! / . C ' ~ ~ / W l l 1 ~ ~ l . 1993. 15x7 15x8

Dow

nloa

ded

by [

Yor

k U

nive

rsity

Lib

rari

es]

at 0

7:28

13

Nov

embe

r 20

14

TAXANE DITERPENOIDS FROM TAXL'S Yti/ViVANPNSZS 79

[ 3 2 ] G. Appendino. H.C. Ozen. I . Fenoglio. P. Garboldi. B. Gabetta and E. Bombardelli. Phi , -

[33] R.P. Doss, J.R. Carney, C.H. Shanks. R.T. Williarnson and J.D. Chamberlain. J . N U I .

[34] J.Z. %hang, Q.C. Fang, X.T. L.iang, C.H. He, M . Kong. W.Y. Hc and X.L. Jin. P / ~ J -

[35] J.Z. Zhang. Q.C. Fang, X.T. Liang and C.€1. He. Chin. CAmm. Lett. 1994. 5. 497-501. [36] G. Appendino, G. Cravotto, R. Enriu, D. Gariboldi. L. Barboni. E. Torregini. G. Gabetta,

G. Zml and E. Bombardelli. J . ~Vur . Prod. 1994. 57, 607-613. [37] D.G.I. Kingston, A..4. Moliiiero and J . M . Rirnoldi. In ProgwJs in rlze Chn77isrr.j. ($Orgun-

ic ~h'uturul Piodurtr. Eds. Herz, W.. Kirby, G.W., Moore, R.E., Steglich, W. and Tamin, C.H.. Springer., 1993, Vol. 61. pp. 1-206.

todimisrry 1993, 33. 1521-1523.

Prod. 1997.60. 1130-1133.

rachcniitry 1995.40. 881-884.

[38] G. Appendino. Nut. Prod. Rep. 1995. 12. 349-360. 1391 M. Sako. H. Sumki. N. Yamamoto. K . Hirota and Y. Maki. J. Cherri. Soc.. Perkin Trms.

1, 1998.714 421.

Dow

nloa

ded

by [

Yor

k U

nive

rsity

Lib

rari

es]

at 0

7:28

13

Nov

embe

r 20

14