acetogenins and styryllactones

7/29/2019 Acetogenins and Styryllactones

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ACETOGENINS AND STYRYLLACTONES

Hilwan Yuda Teruna, PhD

Sekolah Tinggi Ilmu Farmasi Riau

Plants have been utilised for many purposes by humans since

before recorded history. One of the important uses is as a source of

medicinal agents. The first written records of the use of plants for

medicinal purposes dates back to about 2600 BC in Mesopotamia (Balick

and Cox, 1996). Since then, human beings have never stopped

depending on plants for their health.The major sources of plant medicines are from tropical forests. Of

about 250,000 higher plant species, more than half are found in the

tropical rain forests (Soejarto, 1993). Approximately 20,000 plant

species have been recorded as traditional medicines (Soejarto, 1993)

and some 600 botanical items have been recognized in various editions

of The United States Pharmacopoeia (Tyler, 1993).

Styryl-lactones are important constituents in a number ofprimitive families, such as Equisetaceae, Lauraceae, Piperaceae,

Ranunculaceae and Zingeberaceae (Blazquez et al., 1999). The first

styryl-lactone found in the Annonaceae was goniothalamin, isolated

from Goniothalamus andersonii, G. macrophyllus and G. malayanus

(Jewers et al., 1972). This compound had previously been reported from

Cryptocarya caloneura (Lauraceae)(Hlubucek and Robertson, 1967). In

one review, Blazquez (1999) found that Goniothalamus appeared to be

a major producer of styryl-lactones. Figure 1.5 illustrates six types of

styryl-lactones.


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O O

O

OO

O

O O

O

O O O

O

O

O

Styryl-pyrone Furano-pyrone Furano-furone

Pyrano-pyrane Butenolide Heptolide

Figure 1.5: Types of styryl-lactones.

In 1982 Jolad et al. (1982) reported uvaricin (33) the first of a new

group of compounds from the Annonaceae that were believed to be

polyketide derivatives (later they became known as the annonaceous

acetogenin class of compounds). Stereochemistry, absolute or relative,

of the compound was not established at that time (Figure 1.6). This

compound demonstrated potent antitumor activities.

O

O

O

HOH

O

OAc

33.Uvaricin

Figure 1.6: The first annonaceous acetogenin.

The finding of this acetogenin triggered an extensive search for

more of these compounds in annonaceous plants. Numerous

acetogenins have now been isolated with a wide range of biological

effects including pesticidal, fungicidal, antimalarial, antiprotozoal and

antimicrobial activities. Moreover, it appears that annonaceous

acetogenins are distributed in only a limited number of genera within

the Annonaceae (Alali et al., 1999a).

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Until 1997, 39 species from 9 different genera had been reported

to contain acetogenins, Annona (15 species), Asimina (4 species),

Disepalum (1 species), Goniothalamus

(4 species), Polyalthia (1 species), Porcelia (1 species), Rollina (7

species), Uvaria (5 species) and Xylopia (1 species) (Zafra-Polo et al.,

1998). Recently, five more species from Goniothalamus, G. cheliensis

(Li et al., 1997b; Li et al., 1998), G. dolichocarpus (Goh et al., 1995b), G.

gardneri (Chen et al., 1997; Chen et al., 1998b; Seidel et al., 1999), G.

leiocarpus (Mu et al., 1998) and G. velutinus (Ee, 1998) have been

demonstrated to contain acetogenins.

Acetogenins

At least twenty-eight species have been studied and their

constituents are listed in Table 1.2. These phytochemical studieshave

revealed the importance of this genus as a source of styryl-lactones and

acetogenins, with other classes of compounds such as isoquinoline

alkaloids also being significant (Blazquez et al., 1999; Cave et al., 1997;

Waterman, 1993; Zafra-Polo et al., 1996).

Isolation of acetogenins from plant materials is usually started

with extraction with ethanol or methanol. The alcoholic extracts then

are subjected to a series of liquid/liquid partitions with increasing

polarity. Each fraction is monitored by TLC and bioassays such as the

brine shrimp lethality test (BST). Kedde's reagent is used to detect

acetogenins on the TLC plates. Positive fractions are then subjected to

fractionation processes by silica gel columns, circular partition or

preparative HPLC. Many acetogenins exist as epimeric pairs that cannot

be easily separated, although semi-preparative HPLC can sometimes be

successful. Reversed-phase C18 HPLC column gives better result than

normal-phase silica gel (Alali et al., 1999a; Cave et al., 1997).

Countercurrent chromatography has been employed to

concentrate acetogenin fractions. However, further purification with

HPLC is still necessary (Alali et al., 1999a).

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Since 1997, liquid chromatography-electrospray ionization mass

spectroscopy (LC/EIMS) has been introduced to detect acetogenins. The

pattern of fragmentation is reproducible, using the positive-ion mode

and under conditions of atmospheric pressure

in-source collision-induced dissociation (APICID). This technique

produces the spectra that show [M+Na]+ and [M+H]+, as well as the loss

of water molecules [H2O] several times (Gu et al., 1997).

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Table 1.2: Distribution of constituents in the genus

Goniothalamus

Species Type of Constituents

References

G. amuyon Acetogenins, alkaloidsand styryl-lactones

(Lu et al., 1985; Wu et al., 1991; Wu etal., 1992)

G. andersonii Alkaloids and styryl-lactones

(Ee et al., 1998; Jewers et al., 1972;Tanaka et al., 1997)

G. arvensis Styryl-lactones (Bermejo et al., 1995; Bermejo et al.,1998a; Bermejo et al., 1998b)

G. borneensis Alkaloids, a flavonoid, aphenylpropane, a

phytosterol and styryl-lactones

(Cao et al., 1998)

G.cardiopetalus

A phytosterol and styryl-lactones

(Hisham et al., 2000; Hisham et al.,2003)

G. cheliensis Acetogenins, a flavonoid-alkaloid and styryl-lactones

(Gu et al., 2000; Li et al., 1997b; Li et al.,1998; Wang et al., 2002)

G.dolichocarpus

An acetogenin and styryl-lactones

(Goh et al., 1995a; Goh et al., 1995b)

G. donnaiensis Acetogenins (Jiang et al., 1997; Jiang and Yu, 1997a;Jiang and Yu, 1997b; Jiang et al., 1998a;Jiang et al., 1998b; Jiang et al., 1998c)

G. fasciculatus A flavonoid (Zakaria et al., 2000)

G. fulvus A styryl-lactone (Zakaria et al., 1989)G. gardneri Acetogenins (Chen et al., 1997; Chen et al., 1998b;

Chen et al., 1998c; Seidel et al., 1999)G. giganteus Acetogenins and styryl-

lactones(Alali et al., 1997a; Alali et al., 1997b;Alali et al., 1998b; Alali et al., 1999b;Alkofahi et al., 1988; Alkofahi et al.,1990; Fang et al., 1991a; Fang et al.,1991b; Fang et al., 1992a; Fang et al.,1992b; Fang et al., 1993; Gu et al.,1994a; Zeng et al., 1996a; Zeng et al.,1996b; Zhang et al., 1995)

G. grandiflorus Styryl-lactones (Khan et al., 1998; Khan et al., 1999)G. griffithii Alkaloids, a cyclopeptide,

a triterpene, phytosterolsand styryl-lactones

(Alali et al., 1999b; Chen et al., 1998a;Hu et al., 1999a; Hu et al., 1999b; Li etal., 1997a; Mu et al., 2003a; Talapatra etal., 1985a; Talapatra et al., 1985b;Zhang et al., 1993; Zhang et al., 1999a;Zhang et al., 1999b)

G. howii Acetogenins, a styryl-lactone and aphenylpropanoid

(Chen et al., 1998a; Zhang et al., 1993)

G. leiocarpus Acetogenins,cyclopeptides and styryl-lactone

(Mu et al., 1996; Mu et al., 1998; Mu etal., 1999a; Mu et al., 1999b; Mu et al.,2003b)

G.

macrophyllus

Styryl-lactones (Jewers et al., 1972; Sam et al., 1987)

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Table 1.2 (Cont.): Distribution of constituents in the genus

Goniothalamus

Species Type of Constituents

References

G. malayanus Essential oils and styryl-lactones

(Colegate et al., 1990; Inayat-Hussain etal., 2002; Jantan and Ahmad, 2002;Jewers et al., 1972)

G. marcanii Alkaloids and a quinone (Soonthornchareonnon et al., 1999)G. montanus A styryl-lactone (Colegate et al., 1990)G. ridleyi Sesquiterpenes, styryl-

lactones(Ee et al., 1999)

G. scortechinii Alkaloids and a styryl-lactone

(Din et al., 1990; Zakaria et al., 1989)

G.sesquipedalis

An acetogenin, alkaloids,a peptide, phytosterolsand styryl-lactones

(Hasan et al., 1994; Hasan et al., 1995;Hasan et al., 1996; Mia et al., 1997;Talapatra et al., 1985b; Talapatra et al.,1988)

G. tapis Alkaloids, sesquiterpenes,phytosterols and styryl-lactones

(Colegate et al., 1990; Ee et al., 2000;Zakaria et al., 1989)

G. thwaitesii Flavonoids andtriterpenes

(Seidel et al., 2000)

G. umbrosus Styryl-lactones (Ahmad and Din, 2002)G. uvarioides Styryl-lactones (Ahmad et al., 1991)G. velutinus Alkaloids and styryl-

lactones(Ee, 1998)

Structure elucidation of acetogenins is not an easy task. Early

investigations could not establish the absolute stereochemistry of the

compounds. This was because of the complex stereochemistry and

waxy nature of these compounds. However, the application of the

Mosher ester method has helped to determine the relative

stereochemistry of some oxygen bearing carbons. Positions of

tetrahydofuran (THF) and hydroxyl groups can be predicted byanalysing the fragmentation pattern of EI-MS, CI-MS or FAB-MS.

Moreover synthetic models have helped phytochemists to predict the

relative stereochemistry of the THF ring systems, with their flanking

hydroxyls and of the 4-hydroxyled--lactone ring (Alali et al., 1999a). So

far, only gigantecin, a non-adjacent bis-THF acetogenin has yielded to X-

ray analysis (Yu et al., 1994).

In his review McLaughlin (1999) observed that more than 350annonaceous acetogenins had been reported (Alali et al., 1999a). To

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date approximately 400 acetogenins have been isolated. Of the 46-

acetogenins bearing species known in the Annonaceae nine belong to

Goniothalamus (Table 1.3).

Types of acetogenins found in Goniothalamus have been grouped

based on the number of tetrahydofuran (THF) rings, mono-THF, bis-THF,

non-adjacent bis-THF, tri-THF or pyran rings, or the absence of rings

(linear) in the molecules and sub grouped by the form of the -lactone

ring (unsaturated -methyl--lactone, a propanone substituted

unsaturated

-lactone or a -hydroxy--methyl--lactone) (Cave et al., 1997). Figures

1.7, 1.8, 1.9, 1.10, 1.11 and 1.12 show the mono-THF, bis-THF, non-

adjacent bis-THF, pyran and non-THF acetogenins, respectively.

Acetogenins have a wide range of biological activities. Extensive

studies revealed that they have cytotoxic, antitumor, antiparasitic,

pesticidal, antimicrobial, antifungal and immunosuppressive properties

(Alali et al., 1999a; Cave et al., 1997). The structures of acetogenins

are very crucial in terms of their activities. For example, annonacin (42)

has a cytotoxic activity against KB cells ED50 1 x 10-4g/mL, whilst its

ketone derivative, annonacinone showed only 1 x 10-3g/mL (Cave et

al., 1997). Their cytotoxic mechanism is as inhibitors of mitochondrial

complex I (Alali et al., 1999a).

Annonacin (42), howiicin B (70) and howiicin C (46) exhibit a

filaricidal activity against Molidema dessetae (Cave et al., 1997).

Annomontacin (41) and gigantetrocin A demonstrate a pesticidal

activity against some cockroach panels (Alali et al., 1999a). Many

acetogenins, especially of those with unsaturated -hydroxyl--methyl--

lactone rings, have not been tested for their biological activities.

Table 1.3: Acetogenins from the genus Goniothalamus

Species and

Compounds

Type of Acetogenins References

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Goniothalamus amuyonAnnonacin (42) Mono-THF (Li and Chang, 1996)Corossolin (46) Mono-THF (Li and Chang, 1996)Gigantriocin (62) Mono-THF (Li and Chang, 1996)

Goniothalamus cheliensisCheliensisin B (43) Mono-THF (Li et al., 1997b)Cheliensisin C (44) Mono-THF (Li et al., 1997b)

GoniothalamusdolichocarpusAnnonacin (42) Mono-THF (Goh et al., 1995b)

Goniothalamus donnaiensisAnnonacin (42) Mono-THF (Jiang and Yu,

1997a)Isoannonacin (71) Mono-THF (Jiang and Yu,

1997a)

Donbutocin (91) Linear (Jiang et al., 1998c)Donhepocin (92) Linear (Jiang et al., 1998c)

34-epi-Donhepocin Linear (Jiang et al., 1998c)Donhexocin (93) Linear (Jiang and Yu,

1997b)(Jiang et al., 1998c)

Donnaienin (47) Mono-THF (Jiang et al., 1998b)Donnaienin A (48) Mono-THF (Jiang and Yu,

1997a)34-epi-Donnaienin A Mono-THF (Jiang and Yu,

1997a)Donnaienin B (49) Mono-THF (Jiang and Yu,

1997a)34-epi-Donnaienin B Mono-THF (Jiang and Yu,1997a)

Donnaienin C (50) Mono-THF (Jiang et al., 1998a)34-epi-Donnaienin C Mono-THF (Jiang et al., 1998a)

Donnaienin D (94) Linear (Jiang et al., 1998a)34-epi-Donnaienin D Linear (Jiang et al., 1998a)

Table 1.3 (cont.): Acetogenins from the genus Goniothalamus

Species and

Compounds

Type of

Acetogenins

References

2,4-cis-Gigantetrocinone(76)

Mono-THF (Jiang et al., 1997)

2,4 trans-Gigantetrocinone

Mono-THF (Jiang et al., 1997)

Goniodonin (65) Mono-THF (Jiang et al., 1997)Goniothalamicin (68) Mono-THF (Jiang and Yu, 1997a)Murisolin (70) Mono-THF (Jiang and Yu, 1997a)

Goniothalamus gardneriAnnonacin (42) Mono-THF (Chen et al., 1997)Isoannonacin (71) Mono-THF (Chen et al., 1997)

Gardnerilin A (95) Linear (Chen et al., 1998c)Gardnerilin B (96) Linear (Chen et al., 1998c)

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Gardnerin (51) Mono-THF (Chen et al., 1997)Gardnerinin (52) Mono-THF (Chen et al., 1998b)

34-epi-Gardnerinin Mono-THF (Chen et al., 1998b)Gigantetrocin A (54) Mono-THF (Chen et al., 1997)Gigantetrocin B (55) Mono-THF (Chen et al., 1997)

Goniothalamicin (68) Mono-THF (Chen et al., 1997)Goniothalamusin (97) Linear (Seidel et al., 1999)

Goniothalamus giganteusAnnomontacin (41) Mono-THF (Fang et al., 1992a)4-Deoxyannomontacin (45) Mono-THF (Alali et al., 1997b)cis- Annomontacinone (75) Mono-THF (Alali et al., 1997b)

trans-Annomontacinone Mono-THF (Alali et al., 1997b)Annonacin (42) Mono-THF (Alkofahi et al., 1988)2,4-cis-Isoannonacin (78) Mono-THF (Alali et al., 1997a)

2,4-trans-Isoannonacin Mono-THF (Alali et al., 1997a)Asimilobin (80) Adjacent bis-THF (Zhang et al., 1995)Giganenin (53) Mono-THF (Fang et al., 1992b)

Giganin (90) Linear (Fang et al., 1993)Gigantecin (84) Non Adjacent bis-THF (Alkofahi et al., 1990)4-Deoxygigantecin (85) Non Adjacent bis-THF (Fang et al., 1992b)

(Alali et al., 1997a)2,4-cis-Gigantecinone (86) Non Adjacent bis-THF (Alali et al., 1997a)

2,4-trans-Gigantecinone Non Adjacent bis-THF (Alali et al., 1997a)Gigantetrocin (54) Mono-THF (Fang et al., 1991b)4-Acetylgigantetrocin A(54)

Mono-THF (Zeng et al., 1996b)

2,4-cis-Gigantetrocinone(76)

Mono-THF (Alali et al., 1997b)

2,4-trans-

Gigantetrocinone


Gigantetronenin (57) Mono-THF (Fang et al., 1992a)Gigantransenin A (59) Mono-THF (Zeng et al., 1996a)Gigantransenin B (60) Mono-THF (Zeng et al., 1996a)Gigantransenin C (61) Mono-THF (Zeng et al., 1996a)Gigantriocin (62) Mono-THF (Fang et al., 1991b)

(Fang et al., 1991b)Gigantrionenin (63) Mono-THF (Fang et al., 1992a)cis-Gigantrionenin (64) Mono-THF (Zeng et al., 1996b)Goniocin (87) tri-THF (Gu et al., 1994a)Goniodenin (81) Adjacent bis-THF (Zhang et al., 1995)Gonionenin (66) Mono-THF (Gu et al., 1994b)

(Alali et al., 1998b)

2,4-cis-Gonioneninone (77) Mono-THF (Alali et al., 1998b)2,4-trans-Gonioneninone Mono-THF (Alali et al., 1998b)

Goniotetracin (67) Mono-THF (Alali et al., 1998b)

Table 1.3 (cont.): Acetogenins from the genus Goniothalamus

Species andCompounds

Type ofAcetogenins

References

Goniothalamicin (68) Mono-THF (Alkofahi et al., 1988)(Alali et al., 1998b)

Goniotriocin (83) Non Adjacent bis-THF (Alali et al., 1999b)Goniotrionin (69) Mono-THF (Alali et al., 1998a)

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Longicoricin (72) Mono-THF (Alali et al., 1997b)Longifolicin (73) Mono-THF (Alali et al., 1997b)Longimicin C (82) Adjacent bis-THF (Alali et al., 1997a)Pyragonicin (88) Pyran (Alali et al., 1998a)Pyranicin (89) Pyran (Alali et al., 1998a)

Xylomaticin (74) Mono-THF (Alali et al., 1997b)2,4-cis-Xylomaticinone(79)


2,4-trans-Xylomaticinone


Goniothalamus howiiHowiicin A (42) Mono-THF (Zhang et al., 1993)Howiicin B (70) Mono-THF (Zhang et al., 1993)Howiicin C (46) Mono-THF (Zhang et al., 1993)Howiinin D (62) Mono-THF (Chen et al., 1998a)Howiicin E (71) Mono-THF (Yang et al., 1994)Howiicin F (54) Mono-THF (Yang et al., 1994)

Howicin G (55) Mono-THF (Zhang et al., 1993)

Goniothalamus leiocarpusAnnonacin (42) Mono-THF (Mu et al., 1998)Corossoline (46) Mono-THF (Mu et al., 1998)Gigantriocin (62) Mono-THF (Mu et al., 1998)Murisolin (70) Mono-THF (Mu et al., 1998)

GoniothalamussesquipedalisGigantetrocin (54) Mono-THF (Hasan et al., 1996)

Goniothalamus velutinusAnnonacin (42) Mono-THF (Ee, 1998)

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(CH2)nO

OH R3

R2

(CH2)n O

O

R1

Compound NamesNo. ofCarbons

Furan ringandPosition

R1 R2 R3Others andPosition

Sources

Reference

41 Annomontacin 37 er/trans/erat17

H OH OH OH at 10 GGI (Fang et al., 1992a)

42 Annonacin 35 er/trans/erat15

H OH OH OH at 10 GAM (Li and Chang, 1996)

=howiicin A GDO (Goh et al., 1995b)GDN (Jiang and Yu, 1997a)GGA (Chen et al., 1997)GGI (Alkofahi et al., 1988)GHO (Zhang et al., 1993)GLE (Mu et al., 1998)GVE (Ee, 1998)

43 Cheliensisin B 35 At 15 H OH OH OH at 10 & 11,stereochemistrynot stated

GCH (Li et al., 1997b)

44 Cheliensisin C 35 At 15 H OH OH OH at 10,stereochemistrynot stated

GCH (Li et al., 1997b)

Note: er=erythro and th=threo; db=double bond; GAM=G. amuyon, GCH=G. cheliensis, GDO= G. dolichocarpus, GDN=G.donnaiensis, GGA=G. gardneri, GGI=G. giganteus,

GHO=G. howii, GLE=G. leiocarpus, GSE=G. sesquipedalis, GVE=G. velutinus

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Figure 1.7: Mono-THF acetogenins ofGoniothalamus.

(CH2)nO

OH R3

R2

(CH2

)n O

O

R1

Compound NameNo. ofCarbons



Sources

Reference

45 4-deoxyannomontacinA

37 er/trans/erat17

H H OH OH at 10 GGI (Alali et al., 1997b)

46 4-deoxyannonacin=corossolin=howiicin C

35 th/trans/th at15

H H OH OH at 10 GAMGHOGLE

(Li and Chang, 1996)(Zhang et al., 1993)(Mu et al., 1998)

47 Donnaienin 35 er/trans/erat13

H OH OH OH at 10 & 15 GDN (Jiang et al., 1998b)

48 Donnaienin A and 35 er/trans/erat15

OH OH OH mixture GDN (Jiang and Yu,1997a)

34-epi-donnaienin A49 Donnaienin B and 35 trans/erat 9 H OH H OH at 17 & 18 GDN (Jiang and Yu,

1997a)34-epi-donnaienin B (er),mixture GDN

50 Donnaienin C and 37 er/trans/erat15

OH OAc OH OH at 10,mixture

GDN (Jiang et al., 1998a)

34-epi-donnaienin C GDN

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51 Gardnerin 35 er/trans/erat15

H OH OH OH at 8 & 10 GGA (Chen et al., 1997)

52 Gardnerinin and 35 trans/erat 11 OH OH H OH at 10, 19 &20

GGA (Chen et al., 1998b)

34-epi-gardnerinin (er), mixture GGA53 Giganenin 37 th/trans/th at

13H H OH OH at 10 and db

at 21-22GGI (Fang et al., 1992b)



Figure 1.7 (cont.): Mono-THF acetogenins ofGoniothalamus.

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(CH2)nO

OH R3

R2

(CH2)n O

O

R1




Sources

Reference

54 Gigantetrocin=gigantetrocin A=densicomacin-2=howiicin F

35 trans/th at 9 H OH H OH at 17 & 18(th)

GGAGGIGHOGSE

(Chen et al., 1997)(Fang et al., 1991b)(Yang et al., 1994)(Hasan et al., 1996)

55 Gigantetrocin B=howiicin G

35 trans/th at 9 H OH H OH at 17 & 18(th) isomer ofgigantetrocin

GGAGHO

(Chen et al., 1997)(Zhang et al., 1993)

56 4-acetylgigantetrocin A

37 trans/th at 9 H OAc H OH at 17 & 18(th)

GGI (Zeng et al., 1996b)

57 Gigantetronenin 37 trans/erat 9 H OH H OH at 17 & 18(th) cis db at 21-22

GGI (Fang et al., 1992a)

58 Gigantetronin 37 trans/th at 9 H OH H OH at 17 & 18(th)


59 Gigantransenin A 37 er/trans/erat13

H H OH OH at 23 andtrans db at 21-22

GGI (Zeng et al., 1996a)

60 Gigantransenin B 37 er/trans/erat13

H H OH OH at 23 andtrans db at 21-22(23 epimer ofGigantransenin A


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(CH2)nO

OH R3

R2

(CH2)n O

O

R1




Sources

Reference

61 Gigantransenin C 37 er/trans/erat13

H H OH OH at 21 andtrans db at 22-23


62 Gigantriocin=howiicin D

35 trans/th at 9 H H H OH at 17 & 18(th)

GAMGGIGHO

GLE

(Li and Chang, 1996)(Fang et al., 1991b)(Zhang et al., 1993)

(Mu et al., 1998)63 Gigantrionenin 37 trans/th at 9 H H H OH at 17 & 18(th)


64cis-gigantrionenin 37 cis/th at 9 H H H OH at 17 & 18(th)

GGI (Zeng et al., 1996b)

65 Goniodonin 35 er/trans/erat13

OH OH OH OH at 10 GDN (Jiang et al., 1997)

66 Gonionenin 37 th/trans/th at H OH OH cis, db at 21-22 GGI (Gu et al., 1994b)

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13 (Alali et al., 1998b)67 Goniotetracin 37 th/trans/th at

13H OH OH OH at 10 GGI (Alali et al., 1998b)

68 Goniothalamicin 35 th/trans/th at13

H OH OH - GDNGGAGGI

GHO

(Jiang and Yu, 1997a)(Chen et al., 1997)(Alkofahi et al., 1988)(Alali et al., 1998b)(Zhang et al., 1994)




(CH2)nO

OH R3

R2

(CH2)n O

O

R1




Sources

Reference

69 Goniotrionin 35 th/trans/th at 9 H OH H OH at 16, cis db at17-18

GGI (Alali et al., 1998a)

70 Howiicin B=murisolin

35 th/trans/th at15

H OH H - GDNGHOGLE

(Jiang and Yu,1997a)(Zhang et al., 1994)(Mu et al., 1998)

71 Howiicin E=muricatetrocin A

35 At 11 H OH H Stereochemistry isnot stated

GHO (Yang et al., 1994)

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72 Longicoricin 37 er/trans/erat15

H H OH OH at 10 GGI (Alali et al., 1997b)

73 Longifolicin 35 th/trans/th at13

H H OH - GGI (Alali et al., 1997b)

74 Xylomaticin 37 th/trans/th at13

H OH OH OH at 10 GGI (Alali et al., 1997b)




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4

(CH2)mO

OH R

(CH2)n

O1

2

O

O

CompoundName

No. ofCarbons

Position ofFuran ring

R Others and Position Sources

Reference

75Annomontacinone

37; m=11;n=12

At 17 OH OH at 10; mixture of 2,4 cisand trans

GGI (Alali et al., 1997b)

76Gigantetrocinone

35; m=3;n=16

At 9 H OH at 17 and 18 (th)mixture of 2,4 cis and trans

GDNGGI

(Jiang et al., 1997)(Alali et al., 1997b)

77 Gonioneninone 37; m=7;n=14

At 13 OH at 10; cis db at 21-22;mixture of 2,4 cis and trans


78 Isoannonacin 35; m=9;n=10


GDNGGAGGI

(Jiang and Yu,1997a)(Chen et al., 1997)(Alali et al., 1997a)

79 Xylomaticinone 37; m=9;n=12



Note: er=erythro and th=threo; db=double bond; GDN=G. donnaiensis, GGA=G. gardneri, GGI=G. giganteus,


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(CH2)3O(CH2)n

O

OH

9

O

O

OH

R

CompoundName

No. ofCarbons

R Others andPosition

Sources Reference

80 Asimilobin 35; n=12 H - G. giganteus (Zhang et al., 1995)81 Goniodenin 37; n=14 H cis double bond at 21-

22G. giganteus (Zhang et al., 1995)

82 Longimicin C 35; n=12 OH - G. giganteus (Alali et al., 1997a)

Figure 1.8: Bis-THF acetogenins ofGoniothalamus.

9

(CH2)4O(CH

2

)10

O

OH OOH

O

OH

O

CompoundName

No. ofCarbons

Sources Reference

19


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83 Goniotriocin 37 G. giganteus (Alali et al., 1999b)

Figure 1.9: Non-adjacent bis-THF acetogenin ofGoniothalamus.

9

(CH2)4O(CH2)10

O

OH

OHOH

O

R

O


RSources Reference

84 Gigantecin 37 OH G. giganteus (Alkofahi et al.,1990)

85 4-deoxygigantecin 37 H G. giganteus (Fang et al., 1992b)(Alali et al., 1997a)

49

(CH2

)4O(CH2)10

O

OH

OHOH

O

2

OO

Compound Name No. of Others and Sources Reference

20


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Carbons

Position

86 2,4-cis-gigantecinoneand

37 Mixture of cis andtrans

G.giganteus

(Alali et al., 1999b)

2,4-trans-gigantecinone

Figure 1.9 (cont.): Non-adjacent bis-THF acetogenins ofGoniothalamus.

21


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O

O

OH

(CH2)3OOO(CH2)8

OH


Sources Reference

87 Goniocin 37 G.giganteus

(Gu et al., 1994a)

Figure 1.10: Tri-THF acetogenin ofGoniothalamus.

13(CH2)3O

(CH2)12O

O

OH

HO

OH

R2 R1

CompoundName

No. ofCarbons

R1 R2 Source Reference

88 Pyragonicin 37 H OH G.giganteus

(Alali et al., 1998a)

89 Pyranicin 37 OH H G. (Alali et al., 1998a)

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giganteus

Figure 1.11: Pyran acetogenins ofGoniothalamus.

48

OR2R3

R1

R4

1519

R5

R6

R7

R8

(CH2)n

O

CompoundName

No. ofCarbons

R1 R2 R3 R4 R5 R6 R7 R8

OthersandPosition

Sources

Reference

90 Giganin 35;n=11

H H H OH H H H H OH at 17 &18 (er), cis dbat 13-14

GGI (Fang et al., 1992a;Fang et al., 1993)

91 Donbutocin 35;n=11

H OH H OH OH OH H H 15 & 16 th GDN (Jiang et al., 1998c)

92 Donhepocin and 35;n=11

OH OH H OH OH OH OH OH 15 & 16 er; GDN (Jiang et al., 1998c)

34-epi-donhepocin

19 and 20 th

93 Donhexocin 35;n=11

H OH H OH OH OH OH OH 15 & 16 th;19 & 20 th

GDN (Jiang and Yu, 1997b)

94 Donnaienin Dand

37;n=13

OH OAc H OH OH OH OH OH 15 & 16 er; GDN (Jiang et al., 1998a)

34-epi-donnaienin D

19 and 20 er

95 Gardnerilin A 35;n=11

H OH OH H OH OH OH OH 15 & 16 er;19 and 20 er

GGA (Chen et al., 1998c)

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96 Gardnerilin B 35;n=11

H OH H OH H H H H OH at 17 &18 (th)

GGA (Chen et al., 1998c)

Note: er=erythro and th=threo; db=double bond; GDN=G. donnaiensis, GGA=G. gardneri, GGI=G. giganteus

Figure 1.12: Linear acetogenins ofGoniothalamus.

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O

O

CH2OH


Source Reference

97 Goniothalamusin 25 Goniothalamusgardneri

(Seidel et al., 1999)

Figure 1.12 (cont.): Linear acetogenin ofGoniothalamus.

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26


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Styryl-lactones

Styryl-lactones are equally important constituents found in

Goniothalamus. Only five species out of 28 species that have been

studied do not contain styryl-lactones. Their classification is based

on their structure characteristics (Figure 1.5 on page 9). Kedde's

reagent, anisaldehyl-sulphuric acid and phosphomolibdic acid are all

used to detect the compounds on TLC plates. 1D and 2D NMR

experiments are used to elucidate their structures, along with other

spectroscopic methods such as MS, UV and IR. Unlike acetogenins,

X-ray crystallography has been widely used in determining the

absolute stereochemistry (Blazquez et al., 1999).

These compounds possess a wide range of biological activities

such as cytotoxicity, antimicrobial (goniothalamin 98) (Zhang et

al., 1999b), pesticidal (isoaltholactone 119) (Ee et al., 2000) and

embryotoxic (goniothalamin oxide 102) (Sam et al., 1987).

Isolated styryl-lactones known from Goniothalamus, based on their

sources, are listed in Table 1.4. The chemical structures of those

compounds are shown in Figures 1.13, 1.14, 1.15, 1.16, 1.17, 1.18,

1.19 and 1.20 respectively, based on their skeletal types.

Table 1.4: Styryl-lactones from the genus Goniothalamus


Type References

Goniothalamus amuyon7-Acetylgoniodiol (108) Styryl-pyrone (Wu et al., 1991)

(Lan et al., 2003)8-Acetylgoniodiol (109) Styryl-pyrone (Wu et al., 1992)

(Lan et al., 2003)8-Chlorogoniodiol (116) Styryl-pyrone (Lan et al., 2003)5-Deoxygoniopypyrone (132) Pyrano-pyrone (Lan et al., 2003)7,8-diepimer-Goniotriol (114) Styryl-pyrone (Lan et al., 2003)Goniotriol (111) Styryl-pyrone (Wu et al., 1992)

(Lan et al., 2003)Goniothalamin (98) Styryl-pyrone (Lan et al., 2003)Goniothalamin oxide (102) Styryl-pyrone (Lan et al., 2003)8-Methoxygoniodiol (115) Styryl-pyrone (Lan et al., 2003)

Goniothalamus andersonii5-Deoxyisogoniopypyrone Pyrano-pyrone (Ee et al., 1998)

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Type References

(133)Goniodiol (106) Styryl-pyrone (Tanaka et al., 1997)

(Ee et al., 1998)Goniothalamin (98) Styryl-pyrone (Tanaka et al., 1997)Goniothalamin oxide (102) Styryl-pyrone (Ee et al., 1998)

Goniothalamus arvensis3-Acetylaltholactone (122) Furano-pyrone (Peris et al., 2000)5-Acetoxyisogoniothalamin oxide(103)

Styryl-pyrone (Peris et al., 2000)

Table 1.4 (cont.): Styryl-lactones from the genus

Goniothalamus


Type References

Almuheptolide A (141) Heptolide (Bermejo et al., 1998b)Almuheptolide B (142) Heptolide (Bermejo et al., 1998b)Altholactone (119) Furano-pyrone (Bermejo et al., 1995)2-epi-Altholactone (121) Furano-pyrone (Bermejo et al., 1999)Arvensin (126) Furano-pyrone (Bermejo et al., 1999)Etharvendiol (113) Styryl-pyrone (Bermejo et al., 1998a)Etharvensin (125) Furano-pyrone (Bermejo et al., 1997)Garvensintriol (118) Styryl-pyrone (Bermejo et al., 1998a)Goniofufurone (128) Furano-furone (Bermejo et al., 1998a)

Goniotharvensin (124) Furano-pyrone (Bermejo et al., 1995)Isoaltholactone (120) Furano-pyrone (Bermejo et al., 1995)

Goniothalamus borneensisGoniobutenolide A (136) Butenolide (Cao et al., 1998)Goniobutenolide B (137) Butenolide (Cao et al., 1998)Goniofufurone (128) Furano-furone (Cao et al., 1998)Goniothalamin (98) Styryl-pyrone (Cao et al., 1998)Goniothalenol (119) Furano-pyrone (Cao et al., 1998)Goniotriol (111) Styryl-pyrone (Cao et al., 1998)

Goniothalamus cardiopetalusAltholactone (119) Furano-pyrone (Hisham et al., 2000)

Cardiopetalolactone (127) Furano-pyrone (Hisham et al., 2000)Goniopypyrone (131) Pyrano-pyrone (Hisham et al., 2000)Cardiobutanolide (138) Butenolide (Hisham et al., 2003)Goniothalamin (98) Styryl-pyrone (Hisham et al., 2003)Goniodiol (106) Styryl-pyrone (Hisham et al., 2003)Goniofufurone (128) Furano-furone (Hisham et al., 2003)Goniofupyrone (123) Furano-pyrone (Hisham et al., 2003)

Goniothalamus cheliensisCheliensisin A (104) Styryl-pyrone (Li et al., 1998)Goniothalamin (98) Styryl-pyrone (Li et al., 1997b)

Goniothalamus clemensii

5-Acetoxygoniothalamin (99) Styryl-pyrone (Ahmad and Din, 2001)Dehydrogoniothalamin (101) Styryl-pyrone (Ahmad and Din, 2001)

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Type References

Goniothalamin (98) Styryl-pyrone (Ahmad and Din, 2001)

Goniothalamus dolichocarpus5-Deoxyisogoniopypyrone (133) Pyrano-pyrone (Goh et al., 1995b)Goniodiol (106) Styryl-pyrone (Goh et al., 1995b)Goniothalamin oxide (102) Styryl-pyrone (Goh et al., 1995b)Goniothalamin (98) Styryl-pyrone (Goh et al., 1995b)

5--Hydroxygoniothalamin(100)

Styryl-pyrone (Goh et al., 1995a)

Goniothalamus fulvusGoniothalamin (98) Styryl-pyrone (Zakaria et al., 1989)

Goniothalamus giganteus8-Acetylgoniotriol (112) Styryl-pyrone (Fang et al., 1990)Altholactone (119) Furano-pyrone (El-Zayat et al., 1985)

Goniobutenolide A (136) Butenolide (Fang et al., 1991a)Goniobutenolide B (137) Butenolide (Fang et al., 1991a)


Goniothalamus


Type References

Goniodiol (106) Styryl-pyrone (Fang et al., 1991b)Goniofufurone (128) Furano-furone (Fang et al., 1990)8-epi-Goniofufurone (129) Furano-furone (Fang et al., 1991b)Goniofupyrone (123) Furano-pyrone (Fang et al., 1991a)Gonioheptolide A (139) Heptolide (Fang et al., 1993)Gonioheptolide B (140) Heptolide (Fang et al., 1993)Goniopypyrone (131) Pyrano-pyrone (Fang et al., 1990)5-Deoxygoniopypyrone (132) Pyrano-pyrone (Fang et al., 1991b)Goniothalamin (98) Styryl-pyrone (El-Zayat et al., 1985)Goniotriol (111) Styryl-pyrone (Alkofahi et al., 1989)

Goniothalamus grandiflorusIsoaltholactone (120) Furano-pyrone (Khan et al., 1998)

Goniothalamus griffithii8-Acetylgoniotriol (112) Styryl-pyrone (Chen and Yu, 1999)8-Acetylgoniofufurone (130) Furano-furone (Zhang et al., 1999b)7-Acetylgoniopypyrone (135) Pyrano-pyrone (Zhang et al., 1999b)7-Acetylgoniodiol (108) Styryl-pyrone (Zhang et al., 1999b)Altholactone (119) Furano-pyrone (Chen and Yu, 1999)5-Deoxygoniopypyrone (132) Pyrano-pyrone (Chen and Yu, 1999)Goniodiol (106) Styryl-pyrone (Talapatra et al., 1985)Goniodiol diacetate (110) Styryl-pyrone (Talapatra et al., 1985)Goniothalamin (98) Styryl-pyrone (Chen and Yu, 1999)Goniotharvensin (124) Furano-pyrone (Chen and Yu, 1999)Goniofufurone (128) Furano-furone (Chen and Yu, 1999)Goniopypyrone (131) Pyrano-pyrone (Zhang et al., 1999b)Goniotriol (111) Styryl-pyrone (Zhang et al., 1999b)

29


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Type References

Goniodiol (106) Styryl-pyrone (Fang et al., 1991b)Goniofufurone (128) Furano-furone (Fang et al., 1990)8-epi-Goniofufurone (129) Furano-furone (Fang et al., 1991b)Isoaltholactone (120) Furano-pyrone (Zhang et al., 1999b)

Goniothalamus howiiGoniothalamin (98) Styryl-pyrone (Zhang et al., 1993)Howiinin A (105) Styryl-pyrone (Chen et al., 1998)

Goniothalamus leiocarpus7-epi-Goniodiol (107) Styryl-pyrone (Mu et al., 1999b)Goniothalamin (98) Styryl-pyrone (Mu et al., 1998)Leiocarpin A (134) Pyrano-pyrone (Mu et al., 1999b)Leiocarpin B (143) (Mu et al., 1999b)Leiocarpin C (117) Styryl-pyrone (Mu et al., 1999b)

Leiocarpin E (144) (Mu et al., 2004)

Goniothalamus macrophyllus 0Goniothalamin (98) Styryl-pyrone (Sam et al., 1987)Goniothalamin oxide (102) Styryl-pyrone (Sam et al., 1987)

Goniothalamus malayanusIsoaltholactone (120) Furano-pyrone (Colegate et al., 1990)

Goniothalamus montanusIsoaltholactone (120) Furano-pyrone (Colegate et al., 1990)

Goniothalamus ridleyi

Goniothalamin (98) Styryl-pyrone (Ee et al., 1999)Goniothalamin oxide (102) Styryl-pyrone (Ee et al., 1999)


Goniothalamus

Species and Compounds Type References

Isoaltholactone (120) Furano-pyrone (Ee et al., 1999)

Goniothalamus scortechiniiGoniothalamin (98) Styryl-pyrone (Zakaria et al., 1989)

Goniothalamus sesquipedalisGoniodiol (106) Styryl-pyrone (Talapatra et al., 1985)Goniodiol diacetate (110) Styryl-pyrone (Talapatra et al., 1985)Goniothalamin (98) Styryl-pyrone (Hasan et al., 1995)5-Acetoxyisogoniothalamin oxide(103)

Styryl-pyrone (Hasan et al., 1994)

Goniotriol (111) Styryl-pyrone (Talapatra et al., 1985)

Goniothalamus tapisArvensin (126) Furano-pyrone (Ee et al., 2000)

Goniothalamin (98) Styryl-pyrone (Zakaria et al., 1989)Isoaltholactone (120) Furano-pyrone (Colegate et al., 1990)

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Goniothalamus umbrosus5-Acetoxygoniothalamin (99) Styryl-pyrone (Ahmad and Din, 2002)Dehydrogoniothalamin (101) Styryl-pyrone (Ahmad and Din, 2002)Goniothalamin (98) Styryl-pyrone (Ahmad and Din, 2002)

Goniothalamus uvarioides5-Acetylgoniothalamin (99) Styryl-pyrone (Ahmad et al., 1991)Goniothalamin (98) Styryl-pyrone (Ahmad et al., 1991)

Goniothalamus velutinusAltholactone (119) Furano-pyrone (Ee, 1998)Goniothalamin (98) Styryl-pyrone (Ee, 1998)

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O

5

7PhO

R

O7

PhO

I II

CompoundNames

Substitutions

Absoluteconfig.

Sources

Reference

98 Goniothalamin A: R=H 6R GAMGAN

(Lan et al., 2003)(Tanaka et al.,1997)

GBO (Cao et al., 1998)GCA (Hisham et al.,

2000)

GCH (Li et al., 1997b)GDO (Goh et al., 1995b)GFU (Zakaria et al.,

1989)GGI (El-Zayat et al.,

1985)GGR (Chen and Yu,

1999)GHO (Zhang et al., 1993)GLE (Mu et al., 1998)GMA (Sam et al., 1987)GML (Colegate et al.,

1990)GRI (Ee et al., 1999)GSC (Zakaria et al.,

1989)GSE (Hasan et al., 1995)GTA (Zakaria et al.,

1989)GUM (Ahmad and Din,

2002)GUV (Ahmad et al.,

1991)GVE (Ee, 1998)

99 5-Acetoxy-

goniothalamin

A: R=OAc 5S, 6S GUM

GUV

(Ahmad and Din,

2002)(Ahmad et al.,1991)

100 5-Hydroxy-goniothalamin

A: R=OH 5S, 6S GDO (Goh et al., 1995a)

101 Dehydro-goniothalamin

B GUMGCL

{Ahmad, 2002#182{Ahmad, 2001#303}

Note: GAM=G. amuyon, GAN=G. andersonii, GBO=G. borneensis, GCA= G.cardiopetalus, GCH=G. cheliensis, GCL=G. clemensii, GDO=G. dolichocarpus, GFU=G. fulvus,GGI=G. giganteus, GGR=G. griffithii, GHO=G. howii, GLE=G, leiocarpus,

GMA=G. macrophyllus, GML=

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G. malayanus, GRI=G. ridleyi, GSC=G. scortechinii, GSE=G. sesquipedalis,GTA=G. tapis, GUM=G. umbrosus, GUV=G. uvaroides, GVE=G. velutinus

Figure 1.13: Styryl-pyrones ofGoniothalamus.

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O

5

7 PhO

R

O

H

H

CompoundNames

Substitutions

Absoluteconfiguration

Sources

Reference

102 Goniothalaminoxide

R=H 6R, 7S, 8S GAMGANGDOGMAGRI

(Lan et al.,2003)(Ee et al., 1998)(Goh et al.,1995b)(Sam et al.,1987)

(Ee et al., 1999)103 5-Acetoxy-isogoniothalamin

oxide

R=OAc 5S, 6S, 7R,8R

GARGSE

(Peris et al.,2000)(Hasan et al.,1994)

104 Cheliensisin A R=OAc 5R, 6S, 7R,8R

GCH (Li et al., 1998)

105 Howiinin A R=OCinnamoyl

5S, 6R, 7S,8S

GHO

Note: GAM=G. amuyon, GAN=G. andersonii, GCH=G. cheliensis, GDO=G.dolichocarpus, GHO=G. howii, GMA=G. macrophyllus, GRI=G. ridleyi, GSE=G. sesquipedalis

Figure 1.13 (cont.): Styryl-pyrones ofGoniothalamus.

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O

5

7PhO

R1

OR2

OR3

CompoundNames

Substitutions

Absoluteconfig.

Sources

Reference

106 Goniodiol R1=R2=R3=H 6R, 7R,8R

GAN (Ee et al., 1998)

(Tanaka et al., 1997)GCA (Hisham et al., 2003)GDO (Goh et al., 1995b)GGI (Fang et al., 1991b)GGR (Talapatra et al.,

1985)GSE (Talapatra et al.,

1985)107 7-epi-Goniodiol

R1=R2=R3=H 6R, 7S,8R

GLE (Mu et al., 1999b)

108 7-Acetyl-goniodiol

R1=R3=H;R2=Ac

6R, 7R,8R

GAM

GGRGSE

(Wu et al., 1991)(Lan et al., 2003)(Zhang et al., 1999b)

109 8-Acetyl-goniodiol

R1=R2=H;R3=Ac

6R, 7R,8R

GAM (Wu et al., 1992)(Lan et al., 2003)

110 Goniodiol

diacetate

R1=H;

R2=R3=Ac

6R, 7R,

8R

GGR

GSE

(Talapatra et al.,

1985)(Talapatra et al.,1985)

111 Goniotriol R1=OH;R2=R3=H

5S, 6R,7R, 8R

GAM

GGIGGRGSE

(Wu et al., 1992)(Lan et al., 2003)(Alkofahi et al., 1989)(Zhang et al., 1999b)(Talapatra et al.,1985)

112 8-Acetyl-goniotriol

R1=OH;R2=H; R3=Ac

5S, 6R,7R, 8R

GGIGGR

(Fang et al., 1990)(Chen and Yu, 1999)

113 Etharvendiol R1=OEt;R2=R3=H

5S, 6R,7R, 8R

GAR (Bermejo et al.,1998a)

114 7,8-diepimer-Goniotriol

R1=OH;R2=R3=H

5S, 6R,7S, 8S

GAM (Lan et al., 2003)

115 8-Methoxy-goniodiol

R1=R2=H;R3=Me

6R, 7R,8R


116 8-Chloro-goniodiol

R1=R2=H;R3=Cl

6R, 7R,8R


117 Leiocarpin C R1=R2=R3=H

4-hydroxy;3,4 dihydro

6R, 7R,8R

GLE (Mu et al., 1999b)

Note: GAM=G. amuyon, GAN=G. andersonii, GBO=G. borneensis, GCA= G.cardiopetalus, GCH=G. cheliensis, GDO=G. dolichocarpuss, GFU=G. fulvus, GGI=G. giganteus,GGR=G. griffithii, GHO=G. howii, GMA=G. macrophyllus, GML=G.

malayanus, GRI=G. ridleyi, GSC=

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G. scortechinii, GSE=G. sesquipedalis, GTA=G. tapis, GUV=G. uvaroides,GVE=G. velutinus


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O

5

7

PhO

OH

OH

OH

CompoundNames


Sources Reference

118Garvensintriol

5S, 6R, 7S,8S

G. arvensis (Bermejo et al.,1998a)


O 3a

7a

O 3

2O

Ph

OR

Compound

Names

Substituti

ons

Absolut

econfig. Sources Reference

119 Altholactone=goniothalenol

R=H 2R, 3R,3aR, 7aS

GAR

GGIGGRGVE

(Peris et al.,2000)(Bermejo et al.,1995)(El-Zayat et al.,1985)(Chen and Yu,1999)(Ee, 1998)

120 Isoaltholactone R=H 2R, 3S,3aR, 7aS

GARGGN

GGRGRIGMLGMOGTA

(Bermejo et al.,1995)

(Khan et al.,1998)(Zhang et al.,1999b)(Ee et al., 1999)(Colegate et al.,1990)(Colegate et al.,1990)(Colegate et al.,1990)

121 2-epi-Altholactone

R=H 2S, 3R,3aR, 7aS

GAR (Bermejo et al.,1999)

122 3-Acetyl-altholactone

R=Ac 2R, 3R,3aR, 7aS


37


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Note: GAR=G. arvensis, GGI=G. giganteus, GGN= G. grandiflorus, GGR=G.griffithii, GML=G. malayanus, GMO=G. montanus, GRI=G. ridleyi, GTA=G. tapis

Figure 1.14: Furano-pyrones ofGoniothalamus.

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O3a

7a

7

O

O

Ph

OH

HR

CompoundNames

Substitutions

Absoluteconfig.

Sources

Reference

123 Goniofupyrone R=OH 2R, 3R,3aS, 7aS,7R

GCAGGI

(Hisham et al.,2003)(Fang et al.,1991a)

124Goniotharvensin

R=H 2R, 3R,3aR, 7aS

GARGGR

(Bermejo et al.,1995)(Chen and Yu,

1999)125 Etharvensin R=OEt 2R, 3R,

3aS, 7aS,7R


126 Arvensin R=OH 2R, 3R,3aS, 7aR,7R

GARGTA

(Bermejo et al.,1999)(Ee et al., 2000)

Note: GAR=G. arvensis, GCA=G. cardiopetalus, GGI=G. giganteus, GTA=G.tapis

O

O

OH

HOH

PhH

H

Compound Names Sources Reference127 Cardiopetalolactone G. cardiopetalus (Hisham et al.,

2000)

Figure 1.14 (cont.): Furano-pyrones ofGoniothalamus.

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4

6

O

2O

8

Ph

OH

ORO

CompoundNames

Substitutions

Absoluteconfig.

Sources

Reference

128 Goniofufurone R=H 4R, 5S,6S, 7R,8R

GARGBOGCAGCHGGIGGR

(Bermejo et al.,1998a)(Cao et al., 1998)(Hisham et al.,2003)(Wang et al., 2001)(Fang et al., 1990)

(Chen and Yu,1999)129 8-epi-Goniofufurone

R=H 4R, 5S,6S, 7R,8S

GGI (Fang et al.,1991b)

130 8-Acetyl-goniofufurone

R=Ac 4R, 5S,6S, 7R,8R

GGR (Zhang et al.,1999b)

Note: GAR=G. arvensis, GBO=G. borneensis, GCA=G. cardiopetalus, GCH=G.cheliensis, GGI=G. giganteus, GGR=G. griffithii

Figure 1.15: Furano-furones ofGoniothalamus.

4

5

7

O

2

O

O PhR1

OR2

CompoundNames

Substitutions


Sources

Reference

131Goniopypyrone

R1=OH; R2=H 4S, 5S, 6R,7R, 8S

GCAGGIGGR

(Hisham et al.,2000)(Fang et al., 1990)(Zhang et al.,1999b)

132 5-Deoxy-gonio-

pypyrone

R1=R2=H 4R, 6R, 7S,8S

GAMGGIGGR

(Lan et al., 2003)(Fang et al.,1991b)(Chen and Yu,1999)

133 5-Deoxy-isogonio-

pypyrone

R1=R2=H 4R, 6R, 7S,8R

GANGDOGGR

(Ee et al., 1998)(Goh et al., 1995b)(Zhang et al.,

1999b)134 Leiocarpin A R1=R2=H 4R, 6R, 7S, GLE (Mu et al., 1999b)

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8R135 7-Acetyl-gonio-

pypyrone

R1=OH;R2=Ac

4S, 5S, 6R,7R, 8S

GGR (Zhang et al.,1999b)

Note: GAM=G. amuyon, GAN=G. andersonii, GCA= G. cardiopetalus, GDO=G.dolichocarpus, GGI=

G. giganteus, GGR=G. griffithii, GLE=G. leiocarpus. Some numberingsystems are not consistent with this structure

Figure 1.16: Pyrano-pyrones ofGoniothalamus.

2

O

6

Ph

H

OHO

OHO

H

O

Z E

OPh O

OH

HO H

OH

HO

Ph

HO OH

I II

CompoundNames

Absoluteconfig.

Sources

Reference

136 GoniobutenolideA

I:Z GBOGGI

(Cao et al., 1998)(Fang et al.,1991a)

137 GoniobutenolideB

I: E GBOGGI

(Cao et al., 1998)(Fang et al.,1991a)

138 Cardiobutanolide II GCA (Hisham et al.,2003)

Note: GBO=G. borneensis, GCA=G. cardiopetalus, GGI=G. giganteus

Figure 1.17: Butenolides ofGoniothalamus.

2O

7

HO

R2O

R1

O

OH

Ph

CompoundNames

Substitutions

Config. Sources

Reference

41


42/43

139 GonioheptolideA

R1=OH; R2=Me cis/cis/trans/trans/

GGI (Fang et al.,1993)

140 GonioheptolideB

R1=OH; R2=Et cis/cis/trans/trans/

GGI (Fang et al.,1993)

141 AlmuheptolideA

R1=OEt; R2=Et trans/cis/trans/trans/

GAR (Bermejo et al.,1998b)

142 AlmuheptolideB

R1=H; R2=Et cis/trans/trans/

GAR (Bermejo et al.,1998b)

Note: GBO=G. borneensis, GCA=G. cardiopetalus, GGI=G. giganteus

Figure 1.18: Heptolides ofGoniothalamus.

42


43/43

OH

O

Ph O

O

O

O

Ph

HOH

CompoundName

Source Reference

143 Leiocarpin B G. leiocarpus (Mu et al., 1999a; Mu et al.,1999b)

Figure 1.19: A hybrid of a styryl-pyrone and a flavanonefrom Goniothalamus.

O

O

O

O

HO

H H

O

H

H

H

Compound Name Source Reference144 Leiocarpin E G. leiocarpus (Mu et al.,

2004)

Figure 1.20: Styryl-pyrone dimer from Goniothalamus.

acetogenins and styryllactones

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