Diterpenes From Gorgonian Corals

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REVIEW
www.rsc.org/npr | Natural Product Reports
Diterpenes from gorgonian corals

Fabrice Berrueab and Russell G. Kerr*ab
Received 5th December 2008
First published as an Advance Article on the web 25th March 2009
DOI: 10.1039/b821918b
Downloaded by University of Prince Edward Island on 20 December 2012

Published on 25 March 2009 on http://pubs.rsc.org | doi:10.1039/B821918B
Covering: 1995 to April 2008

Gorgonian corals continue to provide a wealth of novel structures, many of which exhibit potentially
useful biological activity. Notably, the families Briareidae, Gorgoniidae and Plexauridae have been
demonstrated to contain a wide variety of natural products including steroids, acetogenins,
sesquiterpenes and diterpenes. The most common of the gorgonian natural products are the diterpenes,
and the intent of this review is to describe such compounds isolated from gorgonian corals, with a focus
on the structures of new compounds as well as their biological activity. There have been developments
improving our understanding of the biosynthetic origin of selected diterpenes, and these will also be
discussed. This review describes 602 new compounds from 177 articles.
1
2
2.1
2.2
2.3
3
3.1
3.2
3.3
3.4
4
4.1
4.2
5
6
Introduction
Suborder Scleraxonia
Family Anthothelidae
Family Briareidae
Family Subergorgiidae
Suborder Holaxonia
Family Acanthogorgoniidae
Family Gorgoniidae
Family Paramucidae
Family Plexauridae
Suborder Calcaxonia
Family Ellisellidae
Family Primnoidae
Conclusions
References
1 Introduction
Gorgonian octocorals (order Gorgonacea) represent a diverse
group of Cnidaria of great interest to the natural products
community. Tropical reefs are often dominated by these organisms, whose taxonomic identifications have been described as
perplexing and often exasperating by F. M. Bayer (1961) the
author of The shallow-water octocorallia of the West Indian
region. Several reviews focused on various aspects of the terpene
chemistry of corals have been published, with the most recent
comprehensive review on gorgonian natural products reported in
1995.1 Gorgonians belong to the class Anthozoa, the subclass
Octocorallia and the order Gorgonacea, which is composed of
a
Department of Chemistry, Atlantic Veterinary College, University of
Prince Edward Island, Charlottetown, Prince Edward Island, C1A 4P3,
Canada. E-mail: rkerr@upei.ca; Fax: +1 902 566 7445; Tel: +1 902 566
0565
b
Department of Biomedical Sciences, Atlantic Veterinary College,
University of Prince Edward Island, Charlottetown, Prince Edward
Island, C1A 4P3, Canada
This journal is The Royal Society of Chemistry 2009
three suborders: Scleraxonia, Holaxonia and Calcaxonia (Fig. 1).

This review is organized phylogenetically, and within each of the
three suborders the families are organized alphabetically.
Suborder Scleraxonia
2.1 Family Anthothelidae

Erythropodium caribaeorum. Erythropodium caribaeorum
continues to provide novel diterpenes with extremely potent
cytotoxic activity such as the eleutherobin and erythrolide
families. Erythrolide K (1), possessing an unusual bicyclic [9.2.1]
tetradecane skeleton, is one such example.2 The structure was
deduced by 2D NMR, confirmed by X-ray analysis and also
synthesized from erythrolide A3 in two steps.2 The study of the
chemical constituents of a collection of E. caribaeorum from
the north coast of Jamaica has resulted in the isolation of three
novel diterpenes (24),4 whose structures were identified from
NMR data as the acetylated derivatives of erythrolydes E, I and
H, respectively.5,6 A bioassay-guided fractionation of an extract
of E. caribaeorum by Andersen and co-workers7 led to the
isolation of six new antimitotic diterpenoids, desmethyleleutherobin (5), desacetyleleutherobin (6), isoeleutherobin A (7),
(Z)-eleutherobin (8), caribaeoside (9) and caribaeolin (10), thus
enlarging this family of highly promising microtubule-stabilizing
agents. Compounds 510, characterized by extensive spectroscopic analysis, showed significant antimitotic activity in cellbased assays.8 Desmethyleleutherobin (5) (IC50 20 nM) and
isoeleutherobin A (7) (IC50 50 nM) were found to be more potent
than eleutherobin (IC50 100 nM).7 Two new natural products,
caribaeorane (11) and 15-hydroxycaribaeorane (12), were identified by the isolation of their C-4 methylketal artifact, which led
to a proposal for the late stages of eleutherobin biosynthesis.9 A
further investigation of a methanol extract of a cultured E. caribaeorum resulted in the isolation of a diterpene with a highly
rearranged carbon skeleton, aquariolide A (13).10
From samples of E. caribaeorum collected at Buccoo Reef
and Flying Reef, Tobago, six new briarane diterpenoids,
erythrolides LQ (1419), were identified.11 The structures and
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relative configurations of these metabolites were elucidated by

interpretation of 2D NMR and MS data. The structure and
stereochemistry of erythrolide P (18) was confirmed by X-ray
crystallographic analysis. Seven new diterpenoids belonging to
the briarane [erythrolides RU (2023)], erythrane [erythrolide

V (24)], and aquariane [aquariolide B (25) and C (26)] classes
have been reported from Dominican samples of E. caribaeorum.12
Fabrice Berru!
e was born in
Tours, France, in 1977 and
graduated in chemistry in 2000
at
the
Ecole
Nationale
Sup!
erieure de Chimie de Montpellier. He received his Ph.D.
from the University of Nice
where he studied the isolation
and purification of novel antitumoral metabolites from marine
sponges. He is currently a postdoctoral researcher with Prof.
Russell Kerr at the University of
Fabrice Berru!e
Prince Edward Island. His
research interests are focused on
the relationship between marine invertebrates and their associated
microorganism community, and the ability of symbiotic microbes
to produce bioactive natural products.
Russell Kerr received his B.Sc.

in chemistry and his Ph.D. in
organic chemistry from the
University of Calgary, and
subsequently worked as a postdoctoral fellow at Stanford
University with Prof. Carl
Djerassi. Kerr joined Florida
Atlantic University in 1991
where in 2003 he established the
Center of Excellence in
Biomedical
and
Marine
Biotechnology. In 2006 he
Russell Kerr
moved to the University of
Prince Edward Island where he
is a Canada Research Chair in Marine Natural Products. His
research focuses on the development of production methods of
bioactive marine natural products and the discovery of new marine
natural products with applications in human health.
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Fig. 1 Cladogram of the order Gorgonacea.
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2.2 Family Briareidae

Gorgonian corals of genus Briareum, which can be found in
Caribbean waters and the West Pacific Ocean, are rich sources
of diterpenoids, including the eunicellin, asbestinane, cembrane,
and briarane classes.1,13 Chemical studies of B. asbestinum,
B. excavatum, B. polyanthes, B. stechei and an unidentified
species of Briareum are described below.
Briareum asbestinum. Four new members of a group of tetracyclic diterpenoids belonging to the eunicellin family, briarellins
AD (2730), and the first representative of a new class of ethercyclized eunicellin diterpene named seco-briarellin (31), were
isolated from B. asbestinum collected at Mona Island, Puerto
Rico.14 Briarellins EI (3236), along with several known diterpenoids of the asbestinane, briarane and eunicellane classes, were
identified from the same organism.15 The structures of briarellins
were established on the basis of spectroscopic data.
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The isolation and the structure determination of briareolate

esters DI (3742) and briareolides J (43) and K (44) were
reported from an investigation of Caribbean specimens of B.
asbestinum. The structures of all metabolites were determined by
2D-NMR spectroscopy, and the structure of compound 37 was
confirmed by X-ray analysis.16 In addition to two known briarane diterpenoids, briareins A and B,17,18 briareins CL (4554)
have been reported from shallow-water colonies of B. asbestinum.19
Cyclobutenbriarein A (55), possessing a novel class of C20
rearranged briarane, was isolated along with five new briarane
diterpenes (5660). The structures of these metabolites were
established on the basis of extensive NMR studies and accurate
mass measurements.20,21
Briareum excavatum. Studies on the chemical constituents of
Briareum excavatum led to the isolation of briarane-type diterpenoids, which have been named excavatolides. Excavatolides

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AM (6173) and excavatolides UZ (7479) were isolated from

gorgonians collected in the southernmost tip of Taiwan.2224 The
structures of these metabolites were elucidated by spectroscopic
and chemical methods. The relative configuration of excavatolides B (62) and U (74) were further confirmed by single-crystal
X-ray analysis. From Western Australian samples, excavatolides
NT (8086) were identified by interpretation of spectroscopic
data.25 The excavatolides were screened for cytotoxicity against
a panel of cancer cells (P388, A549, HT29 and MEL28) and
a wide range of activities reported. Excavatolide M (73) was
reported to have potent activity against P388 cells (ED50 0.001
mg/mL) while A, B, H and I had EC50 values of >50 mg/mL
against this cell line.2224
The structure of ten new briarane diterpenes, briaexcavatolides AJ (8796),26 have been established by spectroscopic
analysis. From Taiwanese samples of B. excavatum, studies have
led to the identification of briaexcavatolides KN (97100),27
OR (101104),28 SV (105108),29 W (109),30 and XZ (110
112).31 The structures of briaexcavatolides B (88), K (97), O (101)
and P (102) were confirmed by X-ray crystallographic analysis. A
wide range of cytotoxicity toward P-138, KB, A-549 and H-19

tumor cell lines was reported. For example, 98 and 102 were
reported to have EC50 values of 0.5 and 0.9 mg/mL respectively
against P388 cells while 97, 99101, 103, 104 and 110112 were
reported to be inactive.
Briantheins AC (113115) have been reported from an
Indonesian sample of B. excavatum, and 113 was shown to
reverse multi-drug resistance in human cell lines (KB-C2) overexpressing P-glycoprotein.32 The structure (including the
stereochemistry) of these compounds was established by 2D
NMR data and application of Moshers method. Investigation of
the chemical constituents of a Taiwanese sample of this gorgonian has afforded eight new briarane-related diterpenoids,
designated briaexcavatins AG (116123).3335 The structural
elucidation of these metabolites was achieved by interpretation
of spectroscopic data and chemical methods, assisted in some
cases by molecular mechanics calculations.
Four new 12-hydroxybriaranes, briaexcavatins IL (124127),
were isolated from cultured B. excavatum collected in a 0.6 ton
tank in Taiwan. The structure of these metabolites was
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elucidated by spectroscopic methods, and the structure of excavatolides C (63) and E (65) were further confirmed by X-ray
crystallography.36
Briareum polyanthes. From the non-polar extract of Bermudan
samples of Briareum polyanthes, a novel diterpene hydrocarbon,
emmottene (128) was isolated, the structure of which was elucidated on the basis of detailed spectroscopic data.37 A study of
a Puerto Rican collection of B. polyanthes afforded thirteen new
eunicellin-type diterpenoids, briarellins 129140 and polyanthellin A (141), along with five asbestinane-related diterpenes
(142146) and one briarane-type diterpene (147).38,39 This study
led to the revision of the structure of four previously reported
asbestinin analogues, asbestinin-10, asbestinin-20, asbestinin-21
and 11-acetoxy-4-deacetoxyasbestinin F.
Briareum spp. Bioassay-guided fractionation of the dichloromethane extract from an unidentified species of Briareum has
afforded two new briarane derivatives, violides A and B (148,
149). The structures of these secondary metabolites were determined on the basis of detailed NMR spectroscopic analysis.40
Three new briarane diterpenoids (150152) were identified from
the same gorgonian species, and compounds 150 and 151
exhibited significant cytotoxicity against the human tumor
cell line P-388 with ED50 values of 0.61 and 1.12 mg/mL,
respectively.41 Analysis of an Indonesian Briareum sp. has led to

the isolation and the structure elucidation of two new briarane
stecholide diterpenes (153154).42 Investigation of bioactive
metabolites from a Briareum sp. collected in the area of Bonotsu,
Kogoshima Prefecture, has led to the isolation of the briaranetype diterpenoids violides CV (155174) and five new structures
related to the violides (175179),4347 their structures being
elucidated by interpretation of spectroscopic and X-ray crystallographic data. Some of these metabolites exhibited moderate
cytotoxicity against the growth of Vero and MDCK cells.
Eighteen new briarane diterpenes, briarlides AR (180197),
were reported from a Briareum sp. collected in Japan at Amami
Oshima, Kogoshima Prefecture. The structures, closely related to
the violides, were established on the basis of detailed spectral
analysis.48 Inhibitory activity against Vero and MDCK cells for
180197 was reported (2.0762.1 and 2.4967.1 mg/mL respectively), with violide B acetate (180) being the most active of this
group. A new polyoxygenated briarane-related diterpene,
briarenol A (198), was isolated from an unidentified species of
Briareum.49
Ten new 8,17-epoxybriarane diterpenoids, briaranolides AJ
(199208), were identified from an unidentified species of Briareum from Okinawa. The structures of these metabolites were
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elucidated by spectroscopic analysis supported by X-ray data.50

A further collection of another unidentified species of Briareum
led to the isolation of three new briarenolides AC (209211).
Compounds 209 and 210 possess a rare 9-ketobriarane moiety
and 211 represent the first example of a briarane possessing
a 20-hydroxy group.51 Further investigation of a Briareum sp,
collected at Bonotsu, Kogoshima Prefecture afforded thirteen
new briarane-type diterpenoids (212224)52,53 closely related to
the briaranolides.
Briareum stechei. An investigation of the crude extract from the
Micronesian octocoral Briareum stechei collected at Mil
Channel, Yap, led to the isolation of 23 new briarane-type
diterpene lactones, named milolides (225247).54,55 The structural
elucidation of these metabolites was achieved by interpretation
of spectroscopic data, and this study led to the revision of the
stereochemistry of the known compound solenolide C (247b).56
2.3 Family Subergorgiidae
Subergorgia reticulata. There has been a single report of the
chemistry of Subergorgia reticulata during the period of this
review. An analysis of S. reticulata collected in Sanya, Hainan
Province, resulted in the identification of the briarane reticulolide
(248).57
3 Suborder Holaxonia
3.1 Family Acanthogorgoniidae
Acalycigorgia inermis. Four new diterpenoids possessing the
xenicane skeleton, acalycixeniolides DG (249252), have been
isolated from Acalycigorgia inermis from Keomun Island, Korea.
These metabolites were identified by the interpretation of spectroscopic data, and compound 251, the most potent of these
metabolites, exhibited cytotoxicity against the human leukemia
cell line K562 with a LC50 of 0.2 mg/mL.58,59 Five new xenicane
metabolites, acalycixeniolides HL (253257), were reported
from a separate collection of A. inermis, and acalycixeniolide I
showed the best cytotoxicity against K562 (LC50 of 1.2 mg/mL).60
In this study, 9-deoxyxeniolide A (258),61 previously reported to
possess antibacterial activity, was also shown to exhibit potent
cytotoxicity against the same cell line (LC50 0.04 mg/mL).
Acalycigorgia sp. A series of eunicillin-type diterpenes was isolated from the octocoral gorgonian Acalycigorgia sp. collected by
the Australian Institute of Marine Science scientists in Thailand.
The structure of compound 259a was determined by 2D NMR
analysis, and a series of homologues with the same terpene core
as 259a but with a fatty acid side chain from 6 to 20 carbons
(259b) were identified using tandem mass spectroscopy.62
3.2 Family Gorgoniidae
Eunicella cavolinii. Massileucellins AC (260262) were isolated
from Eunicella cavolinii harvested near Marseille, France. Identification of the structures, which possess two oxa bridges in the
eunicellane skeleton, was based on NMR and MS data.63
A further chemical investigation of the extracts from Eunicella
cavolinii described above led to the purification and characterization of eight new eunicellane-type diterpenes (263270).64
From an acetone extract of a Mediterranean collection of
Eunicella cavolinii, one new eunicellin-type diterpene (271) was
isolated and identified by interpretation of spectroscopic data.65
Eunicella labiata. Five new diterpenoids belonging to the eunicellan class, labiatamides AB (272273) and labiatins AC
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(274276), were isolated from Eunicella labiata collected off the

coast of Senegal, Western Africa.66 Labiatamides A (272) and B
(273) are unusual amino diterpenoids with N-methyl acetamide
functionalities. Labiatin A (274) is a eunicellan diterpene with an
unprecedented ether linkage between the C-2 and C-6. Labiatin B
(275) exhibited cytotoxic activity against the human colon cancer
cell line HCT-116 with an ED50 of 0.85 mg/mL. A new
cladiellane-type diterpene (277) was isolated from E. labiata
collected at Palmones, Spain.67 The new eunicellin-type diterpenes labiatin D (278) and E (279) were isolated from the organic
extract of a Senegalese collection of E. labiata.68 Labiatin E (278)
exhibited moderate cytostatic activity against the cancer cell line
NSCLC-N6.
Eunicella singularis ( stricta). A study of the Mediterranean
gorgonian Eunicella singularis led to the identification of three
diterpenoids belonging to the eunicellane class (280282),64

whose structures were elucidated based on a detailed spectroscopic analysis.
Leptogorgia alba. The new furanocembranolide leptolide (283)
was isolated from the octocoral Leptogorgia alba collected from
the Pacific coast of Panama.69 The structure was elucidated on
the basis of spectral data and X-ray crystallography.
Leptogorgia gilchristi. Three novel geranylgenanylated alkaloids,
malonganenones AC (284286), were isolated from Leptogorgia
gilchristi collected near Ponto Malongane, Mozambique.
Compound 284 was the first 3,7-disubstituted hypoxanthine to
be discovered from a marine source.70
Leptogorgia sp. The furanocembranolides 287290 were isolated
from an unidentified species of Leptogorgia collected at Jicarita
(Panama).71
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Lophogorgia peruana. An investigation of Lophogorgia peruana

collected in the Gulf of California resulted in the identification of
lophodienone (290), lophodiol A and B (291 and 292), 17-acetoxylophotoxin (293), 15,16-epoxylophotoxin (294), 17-acetoxy15,16-epoxylophotoxin (295), and isoepoxylophodione (296).72
Lophogorgia violacea. The crude extract of a Brazilian gorgonian, Lophogorgia violacea, was demonstrated to exhibit
a powerful chemical deterrence toward consumption by generalist fish carnivores. Bioassay-guided fractionation of the extract
led to the isolation of lophotoxin and two new derivatives (297
and 298).73
Pseudopterogorgia acerosa. In 1982, Fenical and Clardy examined the constituents of Floridian specimens of Pseudopterogorgia acerosa and reported the isolation of the first metabolite
containing the pseudopterane skeleton, pseudopterolide (299).74
Since this investigation, further examination of P. acerosa has
enlarged the pseudopterane and cembrane families with other
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structurally complex and biological significant metabolites.1,75

11-Gorgiacerol (300) was isolated as a minor metabolite from
a P. acerosa specimen collected from Bucoo Reef, Tobago, in
1994.76 During the same period, the structure elucidation of
five new pseudopterane diterpenes, pseudopteradiene (301),
pseudopteradienoic acid (302), 11-pseudopteranol (303), pseudopteranoic acid (304) and diepoxy-gorgiacerodiol (305), were
reported.77 After comparison of the 13C NMR data reported in
the literature, both 11-gorgiacerol (300) and 11-pseudopteranol
(303) were found to share the same spectral data. The natural
product chemistry of a Puerto Rican specimen of P. acerosa has
led to the isolation and the structural determination of alanolide
(306),78 a novel tetracyclic norditerpene which appears to be
biogenetically related to tobagolide.79 A new pseudopteranoid,
b,b-diepoxypseudopterolideMeOH adduct 307, and a rare
norcembranolide diterpene, gorgiacerolide (308), were characterized by detailed spectroscopic analysis in addition to NMR

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spectral comparisons with known pseudopterane and cembrane

models.80 Gorgiacerolide (308) represents the first norcembrane
diterpene isolated from a species of Pseudopterogorgia.
A bioassay-guided isolation of the 2-propanol extract of
P. acerosa harvested in Saint Pierre (Martinique) afforded a new
cembranolide (309) as well as pseudopterolide (299).81 The
reported coexistence in P. acerosa of pseudopteranoids and
cembranoids supports the theory that metabolites belonging to
these skeleton classes are intimately related biogenetically.82
Acerolide (309) showed moderate cytotoxicity against a panel
of 14 different tumor cell lines, with the best GI50 of 2.94 mM
against A459. A new tetracyclic pseudopterane alkaloid,
aceropterine (310), was isolated from a collection of P. acerosa in
Puerto Rico.83
Pseudopterogorgia bipinnata. Five new diterpenoid lactones from
Pseudopterogorgia bipinnata with an uncommon gersolane ring
system showed differential antitumor activity in NCIs 60-cellline tumor panel.84 These metabolites (311315), named
pinnatins, are highly functionalized polycyclic a,g-disubstituteda,b-unsaturated-g-lactones, and their structures, which feature
a unique bicyclic [11.1.0] carbon skeleton, were determined
by 2D NMR analysis and confirmed by single-crystal X-ray
diffraction experiments. Irradiation experiments in acetonitrile
suggested a biogenic relationship between the cembrane and
gersolane classes of diterpenes.85 A study of the hexane extract of
P. bipinnata has led to the isolation of an unprecedented heptacyclic C40 bis-diterpenoid, bisgersolanolide (316).85 The structure
was established by detailed spectral analysis and confirmed by
synthesis by a DielsAlder dimerization of two equivalents of
pinnatin C (312).
In 1999, eight new highly oxygenated cembranolide diterpenes,
bipinnatins GI (317319), bipinnatolides FJ (320324), and
a new pseudopteroid, bipinnapterolide A (325), with the rare 2,3epoxy-1,4-dione moiety, were reported from P. bipinnata
collected off San Andres Island, Colombia. Their structures were
determined through a combination of spectroscopic and X-ray
crystallographic methods.86 From the same location, two new
diterpenes a seco-furanocembranolide (326) and the highly
oxygenated cembranolide bipinnatolide K (327) were isolated
and identified by detailed spectroscopic methods.87 An investigation of P. bipinnata collected near San Andres Island
(Colombia) has resulted in the identification of a new diterpene
named verrilin (328), which possesses the novel verrillane carbon
skeleton.88
In 2000, a report described the novel bisditerpenoid ether
biskallolide A (329), which appears to be produced by dehydration of two units of kallolide A (330).88 This report also
indicated that 2-C-alkoxylation and 2-C acyloxylation of kallolide A occur spontaneously in certain solvents. The chemical
structures of kallolide A (330) including the dimeric ether 329
were established by detailed analysis of the spectral data and
comparisons with kallolide A.89 The structures of six new bilactone diterpenoids, caucanolides AF (331336), were elucidated
on the basis of spectroscopic data. Caucanolide A (331) and D
(334) demonstrated significant in vitro antiplasmodial activity
against chloroquine-resistant Plasmodium falciparum W2 with an
IC50 value of 15 mg/mL.90 Moreover, caucanolide B (332)
constitutes the only example from Nature of a secondary
metabolite possessing N1,N1-dimethyl-N2-acylformamidine
functionality. A unique oxapolycyclic diterpenoid, bipinnapterolide B (337), was purified from Colombian samples of
P. bipinnata collected from Old Providence Island. The structure
was deduced from 2D NMR studies and confirmed by singlecrystal X-ray diffraction.91 Compound 337 exhibited moderate
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antituberculosis activity against Mycobacterium tuberculosis

H37RV.
Pseudopterogorgia elisabethae. Since the pioneering work of the
Fenical group in the 1980s,92,93 the molecular architecture and
potent pharmacological activities of the pseudopterosins from
the Caribbean gorgonian Pseudopterogorgia elisabethae has
sparked great interest.1,94 These metabolites represent a family of
diterpene glycosides with the amphilectane skeleton isolated
from P. elisabethae collected in various regions in the Caribbean
and Florida. Pseudopterosins are of considerable interest given
their commercial market as additives in skin cream products
and the successful completion of clinical trials as a topical antiinflammatory agent. In 1998, a report indicated that the mechanism of in vivo analgesic and anti-inflammatory activity of the
pseudopterosins is a consequence of in vivo inhibition of eicosanoid release.95
To date, pseudopterosins have been identified from specimens
collected in the Bahamas,92,96 Bermuda,97 the Florida Keys98 and
Colombia.99,100 During the period covered by this review, three
new pseudopterosins MO (339341) and the three seco-pseudopterosins EG (342344), together with the new amphilectane
derivative elisabethol (345), have been reported from Florida
Keys specimens.98
In 2004, three different research groups reported the isolation
of pseudopterosins from P. elisabethae. Several structures have
been described with an identical name. Firstly, the chemical
studies of an extract of a Colombian specimen (Providencia
Island) afforded seven new pseudopterosins PV (346352).99
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From two collections of P. elisabethae collected from Old

Providence Island and San Andres Island, pseudopterosins PZ
(353363) and seco-pseudopterosins H (364) and I (365) were
reported by a separate group.100 Lastly, a third group reported
the isolation of pseudopterosins P (366) and Q (367) from the
methanol extract of P. elisabethae collected from the Bahamas.97 Some of these new metabolites displayed strong antituberculosis, antiviral, antimalarial, and anticancer activity.
Compounds 366 and 367 were reported to exhibit antibacterial
activity selectively against the Gram-positive bacteria Streptococcus pyogenes, Staphylococcus aureus, and Enterococcus
faecalis.96 Elisabethins E (368) and F (369), were reported
along with 366 and 367 from the Bahamian collection of
P. elisabethae.96 The isolation of the three new non-glycosylated
diterpenes 370372 and the novel seco-pseudopterosin K (373)
were reported in 2006.101
In a series of biosynthetic studies, a combination of radioactivity-guided isolations and detailed NMR-guided searches led to
the proposed biosynthetic pathway for pseudopterosins shown
in Scheme 1.102 The radioactivity-guided approach was used
following an incubation with [3H-C1] geranylgeranyl diphosphate to identify the diterpene cyclase product as elisabethatriene
(374).103 A subsequent report104 described the aromatization of
the cyclase product to give the known metabolite erogorgiaene
(375).105 Oxidation products of this aromatic hydrocarbon were
shown to be 7-hydroxyerogorgiaene (376)105 and 7,8-dihydroxyerogorgiaene (377).106 One of the more intriguing aspects of
pseudopterosin biosynthesis is the nature of the ring closure from

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the serrulatane ring system to the amphilectane skeleton. Secopseudopterosins were shown to be precursors in pseudopterosin
biosynthesis, and their dehydro-derivatives, the amphilectosins,
were demonstrated to be the key intermediate linking these two
classes of diterpenes.107 This study also provided an explanation
for the occurrence of pseudopterosins with a- and b-isobutenyl
substituents. cis-Amphilectosin (378) gave rise specifically to
a pseudopterosin with the b-isobutenyl group, while the transderivative (379) afforded the a-isobutenyl pseudopterosin 380
in biosynthetic experiments. Elisabethatrienol (370) has been
reported from a specimen of P. elisabethae collected in Colombia,101 suggesting that this may be involved in the conversion of
the cyclase product (374) to erogorgiaene; however, this has not
been confirmed experimentally.
The question of the inducibility of diterpene biosynthesis in
gorgonians has been addressed in two systems. Firstly, various
biological and physical stresses were evaluated as potential

inducers of pseudopterosin biosynthesis in Pseudopterogorgia
elisabethae.108 Specifically, data indicated that the production of
pseudopterosins can be significantly increased in response to high
levels of predation by the mollusk Cyphoma gibbosum and in
response to decreased levels of UV/visible radiation. High levels
of feeding by Chaetodon capistratus and artificially wounding of
the gorgonian did not lead to increased pseudopterosin levels.
Following reports of the production of diterpenes by a dinoflagellate preparation of gorgonians,109,110 which demonstrated that
terpene biosynthesis can occur in the absence of the gorgonian
host, the inducibility of diterpenes was investigated in a microbial preparation of two corals.111 This study concluded that
diterpene biosynthesis can be markedly increased through the
addition of plant bioactive substances including methyl jasmonate, salicylic acid and gibberellic acid.
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Scheme 1 Proposed biosynthesis of pseudopterosins.
In 1998, four unusual diterpenes were isolated from

P. elisabethae as representatives of several new classes of previously undescribed natural products, each possessing a novel
carbon skeleton. The structure of novel metabolites elisabethins
AC (381383) and elisabanolide (384) were proposed on the
basis of spectral data analysis, chemical transformations and
X-ray crystallographic analysis.112 Elisabethin B showed significant antitumoral activities against NCIs 60-cell-line tumor panel
and compounds 383 and 384 showed weak in vitro anti-tuberculosis activity.
As a part of a screening for marine natural products with antituberculosis activity, a bioassay-guided fractionation of a West
696 | Nat. Prod. Rep., 2009, 26, 681710
Indian collection of P. elisabethae led to the isolation of two

diterpenoid alkaloids with an uncommon benzoxazole moiety:
pseudopteroxazole (385) and seco-pseudopteroxazole (386).113 A
related metabolite, homopseudopteroxazole (387), was isolated
as a minor constituent of the hexane extract; 385 and 387 were
shown to be strong growth inhibitors of Mycobacterium tuberculosis H37Rv.114 Elisabatins A (388) and B (389) are two novel
amphilectane type diterpenoids isolated from hexane extracts of
P. elisabethae collected in San Andres Island, Colombia.115 The
a configuration assigned to the isobutenyl side chain in
elisabatins A and B distinguishes these metabolites from other
amphilectanes previously isolated from P. elisabethae.92,97,116

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The structures of two novel nor-diterpenes, sandresolides

A (390) and B (391),117 and colombiasin A (392)118 (with
a previously undescribed tetracyclic carbon skeleton) were
reported by Rodriguez and co-workers. The isolation and the
structure elucidation of elisapterosins A (393) and B (394),
possessing the unprecedented elisapterane carbon skeleton, were
reported in addition to elisabethin D (395), elisabethin D acetate
(396) and a new elisabane nor-diterpene, 3-epi-elisabanolide
(397).119 Elisapterosin B displays strong in vitro anti-tuberculosis
activity. Two new tricyclic lactones, elisabetholide (398) and
amphilectolide (399), were reported from a Colombian specimen
of P. elisabethae.120
The study of the chemical constituents of a collection of
P. elisabethae from the Florida Keys has resulted in the isolation
of a novel diterpene alkaloid, elisabethamine (400), which
exhibited modest cytotoxicity against lung and prostate cancer
cell lines.121 12-Acetoxypseudopterolide (401) was identified from
the non-polar fraction of the methanolic extract of P. elisabethae
from the same location, indicating an interesting departure from
the structures of the previously characterized diterpenes from
this gorgonian.122 From West Indian collections of P. elisabethae,
two diterpenoids, cumbiasins A (402) and B (403), possessing
the novel cumbiane tetracyclic framework, were described in
addition to cumbiasin C (404), which has a seco-cumbiane
carbocyclic skeleton.123 The structures and relative configurations of cumbiasins were elucidated by interpretation of
2D-NMR and mass spectroscopic data.
In 2000, elisabatin C (405) and p-benzoquinone 406 were
reported as new representatives of the amphilectane and
serrulatane families of diterpenes, respectively. In addition,
elisapterosin C (407) and two new related amphilectane nor- and
tetrisnor-diterpenes, 4-(acetyl)amphilectolide (408) and amphiphenalone (409), were identified from the same organism.124 In
2003, the structures of elisabatin C (405) and elisabatin B (389)
were established by X ray analysis.115 A novel C40 bisditerpene
(410) was reported to co-occur with erogorgiaene (375) and
7-hydroxyerogorgiaene (376).105 The bisditerpene is apparently
derived from the alcohol 376.
A new diterpene possessing an unprecedented perhydroacenaphthene carbon skeleton was isolated and characterized
by combined spectroscopic data. This compound, named ileabethin (411), contains a fully substituted aromatic ring, whose
substitution pattern resembles that of the pseudopterosin class of
diterpene glycosides. Moreover, the isobutenyl side chain typically found in P. elisabethae metabolites appears in 411 masked
as a spiro gem-dimethyldihydrofuran moiety.125 The structure
and synthesis of a novel serrulatane diterpene, O-methylelisabethadione (412), has been reported.126 This publication also
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indicated that the structure of the previously described

elisabethadione was likely mis-assigned. Two new diterpenes
possessing the rare elisapterane framework were identified
from a Colombian specimen of P. elisabethae. The structures of
elisapterosins C (413) and D (414) were elucidated on the basis
of spectroscopic data and comparisons with known elisapterane
models.127
Ileabethoxazole (415), a new perhydroacenaphthene-type
diterpene alkaloid containing a benzoxazole moiety, has been
reported to display activity against Mycobacterium tuberculosis
(H37Rv).128 Two new norditerpenes, containing a previously
undescribed C19 framework, were identified from two specimens
from a location in the San Andres Archipelago. Caribenols
A (416) and B (417) were elucidated by a combination of single-
698 | Nat. Prod. Rep., 2009, 26, 681710
crystal X-ray analysis and comprehensive 2D NMR measurements.129

Pseudopterogorgia kallos. In 1985, Look et al. reported the first
investigation of the gorgonian Pseudopterogorgia kallos, which
described four new pseudopterane diterpenes kallolide A (330),
kallolide A acetate, kallolide B and kallolide C.130 Eighteen years
after this publication, a novel rearranged pseudopterane, kallosin A (418), was characterized based on detailed spectroscopic
analysis and single-crystal X-ray diffraction studies.131 The
structure of a highly oxygenated hexacyclic diterpene, providencin (419), was established through spectroscopy supported
by X-ray diffraction analysis,132 and demonstrated to exhibit
moderate cytotoxicity against human breast (MCF7), lung
(NCI-H460), and CNS (SF-268) cancer cell lines. From the same

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species, a novel rearranged cembrane diterpene, ciereszkolide

(420), was isolated and identified by interpretation of NMR
and X-ray crystallographic data.133 The structure of another
highly oxygenated hexacyclic diterpene, bielschowskysin (421),
was reported from a chemical study of P. kallos.134 Bielschowskysin (421) was shown to exhibit antimalarial activity
against Plasmodium falciparum as well as strong anticancer
activity against the EKVX non-small-cell lung cancer (GI50 <
0.01 mM) and CAKI-1 renal cancer (GI50 0.51 mM). A novel
trispiropentacyclic diterpene with an unprecedented carbon
skeleton, intricarene (422), was identified by interpretation of
2D-NMR, HREIMS and X-ray diffraction analysis.135 Pattenden and co-workers completed a biomimetic synthesis of this
complex diterpene from bipinnatin J, which itself was
produced in an asymmetric synthesis. The biomimetic production of 422 suggests that this diterpene may be generated from
oxidation of the bipinnatin skeleton followed by a [5 + 2]
cycloaddition.136
Parallel chemical investigations of extracts of P. bipinnata and
P. kallos have resulted in the discovery of seven new pseudopterane class diterpenoids. The structural elucidation of
kallolides DI (423428) and kallolide C acetate (429) was
achieved by spectroscopic methods, and in some instances by
X-ray crystallography.137 Seven new cembranolides, bipinnatins
KQ (430436), were isolated from P. kallos collected off Old
Providence Island, Colombia.138
3.3 Family Paramucidae
Muricella sp. A chemical investigation of two morphologically
distinct populations of gorgonians of the genus Muricella
collected from Jaeju Island, Korea, led to the identification of
two novel diterpenoids (437 and 438) belonging to the cladiellane
class.139 Two years later, a new diterpene, muricellin (439), was

isolated from a species of Muricella collected from the same
region of Korea.140
3.4 Family Plexauridae
Eunicea calyculata. A new dolabellane diterpenoid (440) was
isolated from the gorgonian Eunicea calyculata. The structure
and the relative stereochemistry were elucidated on the basis of
the 1D and 2D NMR data.141
Eunicea laciniata. From the octocoral Eunicea laciniata collected
off the coasts of Palamino Island, Puerto Rico, five new
dolabellane-type diterpenoids (441445) were identified.142 A
chemical investigation of E. laciniata harvested along the coast of
Barbados afforded a new cubitane diterpenoid (446).143 A new
7,8-epoxydolabella-3(E)-12(18)-diene (447) was reported from
a Honduran sample of E. laciniata.144
Eunicea mammosa. A chemical investigation of the crude extract
of a Puerto Rican collection of Eunicea mammosa has resulted
in the isolation of thirteen new cembranolide diterpenoids,
uprolides 448460.145 The structure elucidation was based on
extensive NMR analysis and chemical interconversions, while
the structure of 448 was confirmed by X-ray diffraction analysis.
From the same specimen collected at Mona Island, Puerto Rico,
five new cembranolides (461465) possessing a rare 4,7-oxabridged functionality were isolated.146 The structures were
deduced from extensive spectroscopic data and by chemical
correlation experiments. These new uprolides (461465) displayed moderate cytotoxic activity against the Hela cell line with
IC50 values from 2.5 to 5.1 mg/mL. Three new diterpenes (466
468) possessing a cembrane type skeleton were isolated from the
gorgonian E. mammosa collected in the Bahamas.147 Structure
activity relationship studies were performed on a series of
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synthetic analogues and one of them, possessing two epoxide

moieties, displayed antitumor activity with a ten-fold increase
over the natural homologues.139
Eunicea pinta. In 2002, the first chemical investigation of the
gorgonian octocoral Eunicea pinta led to the isolation and the
structure determination of eight new g-cembranolide-type
diterpenes (469476).148 This study led to the revision of the
structures of several uprolide-type cembranolides described
previously.145,146 Compounds 469 and 470 showed strong
700 | Nat. Prod. Rep., 2009, 26, 681710
cytotoxic activity against several cancer cell lines from the NCI
60 cell-line tumor panel.
Eunicea tourniforti. Five new diterpenoids (477481) were
isolated from the gorgonian Eunicea tourniforti collected off the
southwest coast of St. Thomas, US Virgin Islands, elucidation
of their structures being achieved by interpretation of 1D and
2D NMR data.149 From collections of E. tourniforti along the
southwest coast of Barbados, four new cembrane diterpenes
(482485) were reported.150

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Eunicea sp. Three new diterpenoid glycosides, calyculaglycosides

AC (486488) were isolated from the Caribbean gorgonian
Eunicea sp.151 Calyculaglycosides AC demonstrated efficacy in
several models of inflammation. Two new compounds possessing
a glycosylated cembrane skeleton (489 and 490), as well as a new
cembrane alcohol (491), were isolated from the same species of
Eunicea.152 This study also described a revision of the structures
of calyculaglycosides AC (486488) with the updated structures
reported herein. From an undescribed species of Eunicea
collected in Old Providence Island off Colombia, five new
representatives of the cembrane family of diterpenes (492496)
were isolated as minor metabolites.153 The structure of 492 was
established by X-ray diffraction analysis, and structures for 493
496 then proposed based upon 2D NMR data comparisons
with 492. Compounds 492, 493 and 495 showed significant
antiplasmodial activity against Plasmodium falciparum.153
Eunicea succinea. Investigation of the gorgonian Eunicea succinea collected from Mona Island, Puerto Rico, led to the isolation
of eleven cembrane-type diterpenes (497507) and one new
geranylgeraniol derivative (508). The chemical structures of these
new diterpenoids were established by extensive spectroscopic

analysis.154,155
Euplexaura nuttingi. Six new tetraprenylated purine alkaloids,
designated nuttingins AF (509514), were isolated together with
five new malonganenones DH (515519) from the gorgonian
Euplexaura nutingi collected from Pemba Island, Tanzania.156
These metabolites displayed significant inhibitory activity
against both K562 and UT7 tumor cell lines.
Suborder Calcaxonia
4.1 Family Ellisellidae

Ellisella robusta. Five new chlorinated metabolites featuring the
briarane skeleton, designated robustolides AE (520524), have
been reported from Ellisella robusta collected off the coast of
southern Taiwan.157,158 The absolute stereochemistry of robustolides A (520) and D (523) was established by X-ray diffraction
analysis. From a separate analysis of E. robusta, two new 11,20epoxybriaranes (525 and 526)159 were reported on the basis of
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spectroscopic evidence, and subsequently named robustolides

F and G.157 Robustolide H (527) was later reported from the
E. robusta as an additional member of this family.158
Ellisella sp. A study of Ellisella sp. collected in Okinawa led to the
isolation of four new briarane-type diterpenes (528531) closely
related to the robustolides. Compounds 523 and 524 induced
formation of multinuclear cells at concentrations between
0.5 and 2 mg/mL against NBT-II cells, indicating inhibition of
cytokinesis.160
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Gorgonella umbraculum. A new briarane diterpene, umbraculolide A (532), was isolated from Gorgonella umbraculum collected
from Tuticorin, India.161 A second collection of G. umbraculum
collected from Tamil Nadu, India, led to the isolation of three
new umbraculolides BD (533535), which were characterized by
interpretation of spectroscopic data.162
Junceella fragilis. Gorgonian corals of the genus Junceella are
common in the subtropical and tropical waters of the IndoPacific Ocean and are well known as a source of highly oxidized

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diterpenes of the briarane class.163 The methanol extract of an

Indonesian collection of Junceella fragilis afforded four new
briarane diterpenes (536539). The structure of these new
compounds was established on the basis of extensive NMR
studies, and a modified Mosher method was used to determine
the absolute configuration.164 Junceellolides EG (540542) were
isolated from J. fragilis collected at Green Island, located on the
southeast coast of Taiwan.165 All structures were characterized
by detailed NMR studies, and the relative configuration of junceellolide E (540) was further confirmed by single-crystal X-ray
analysis. The chemical investigation of another collection of
J. fragilis led to the isolation of junceellolide H (543).166 The
structure of a new briarane-type diterpenoid (544), isolated from
J. fragilis, was established based on spectroscopic and chemical
methods.167 Novel diterpenes junceellolide I (545), fragilide
A (546), junceelin (547) and praelolide (548) were isolated
from samples of J. fragilis collected off the southern Taiwan
coast.168170 Chemical investigation of J. fragilis collected from

the South China Sea resulted in the isolation of junceellonoids
A (549) and B (550).171 The structures and relative configurations
of these new metabolites were elucidated by interpretation of
spectroscopic data.
Three new briarane-type diterpenes, junceellonoids CE (551
553) were purified from South China Sea samples of J. fragilis,172
and a study of the chemical constituents of Taiwanese samples of
J. fragilis has resulted in the isolation of three new 11,20-epoxybriarane diterpenoids, junceellolides JL (554556).173 The
structure of 554 was further confirmed by single-crystal X-ray
diffraction analysis. Samples of J. fragilis collected from Papua
New Guinea led to the isolation of two new briarane diterpenoids
(557 and 558),174 and a further study of a collection of J. fragilis
from Taiwan led to the isolation of frajunolides AD (559
562).175 Three new briarane-type diterpenoids, fragilides
BD (563565), were also isolated from Taiwanese samples of
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J. fragilis collected off the southern coast of Taiwan from three

different collections.36,176,177
Junceella gemmacea. There is a single report of terpenes from
Junceella gemmacea. Four new briaranes, nui-inoalides AD
(566569) were isolated from this species of Junceella collected in
Pohnpei and Ant Atoll, Micronesia.178
Junceella juncea. A chemical investigation of the Indian Ocean
gorgonian Junceella juncea resulted in the isolation of eight new
briarane-type diterpenoids, juncins GN (570577), the structures being elucidated by extensive spectroscopic analysis.179181
A bioassay-guided fractionation of the acetone extract of
a Taiwanese collection of J. juncea led to the identification of
seven new diterpenoids, juncenolide AG (578584).182185 Their
704 | Nat. Prod. Rep., 2009, 26, 681710
structures were established by the interpretation of 2D-NMR

spectroscopic data, and the structure of compound 578 was
confirmed by X-ray analysis.
Thirteen new briarane diterpenes, juncins OZI (585597),
were isolated from the EtOH/CH2Cl2 extract of a South China
Sea sample of J. juncea; a structureactivity relationship study
was described, and compounds 588597 were shown to exhibit
potent antifouling activities.186,187 Three new 8-hydroxybriarane
diterpenoids, junceals AC (598600), were recently reported
from a chemical investigation of J. juncea collected off the
southern Taiwan coast,177 and these metabolites were found
to exhibit inhibitory effects on superoxide anion generation by
human neutrophils.

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4.2 Family Primnoidae
Plumarella sp. The first chemical study of a gorgonian belonging

to the genus Plumarella has resulted in the isolation of two new
diterpenes designated as plumarellide (601) and the ethyl ester of
plumarellic acid (602). Their structures were established by
extensive spectroscopic analysis.188
Diterpenes from gorgonian corals continue to provide great

interest to the natural products community. During the period
covered by this review (1995 to April 2008) there were a total of
177 publications focused on diterpenes from gorgonian corals.
Fig. 2 provides a graphical depiction of the numbers of
Conclusions
Fig. 2 Numbers of publications for each species of gorgonian.
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genera Briarium and Junceella have also received considerable

attention. This interest by the scientific community is presumably
due to the significant biological activity of metabolites from these

publications from each species discussed in this review. It is

evident from this graph that the genus Pseudopterogorgia has been
the subject of the greatest number of investigations; however, the
Fig. 3 Diterpene classes of natural products isolated from gorgonians.
706 | Nat. Prod. Rep., 2009, 26, 681710

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genera and likely also a consequence of the high natural abundance of these gorgonians in accessible reef habitats. A range of
biological activities have been reported for diterpenes derived
from gorgonians over the past 13 years, including: anti-cancer
(most common), anti-inflammatory, antiplasmodial, antibacterial, antiviral, antimalarial and antioxidant, as well as ecologically
relevant activities such as fish-feeding deterrence.
There is substantial structural diversity of diterpenes isolated
from gorgonians. Compounds reported during the period
covered by this review can be classified as belonging to one of
40 skeletal classes (Fig. 3). While some of these natural products
were previously known, a substantial number represent new
classes of diterpenes unique to organisms of the marine environment. The classification of diterpenes in the terpene literature
is somewhat confusing and many new compounds are very
similar to ones previously identified.
These classes of diterpenes contain carbocyclic rings with 3, 4, 5,
6, 7, 8, 9, 10, 11, 12, 13 and 14 carbons as well as acyclic skeletons
with novel branching patterns, indicating significant diversity in
terpene biosynthesis in gorgonians. Fig. 4 shows the distribution
of the nine most common carbon skeletal types (amphilectane,
briarane, cembrane, cladiellane, dolabellane, gerenylgeranane,
pseudopterane, serrulatane and xenicane) amongst the genera
studied. Details of the skeletal types isolated from the genus
Pseudopterogorgia clearly the source of the greatest structural
diversity are shown in Fig. 5. Examples of diterpenes spanning
28 of the 40 diterpene classes have been isolated from
Pseudopterogorgia spp. during the time-frame of this review.
There are interesting correlations between certain phylogenetic
groups of gorgonians and classes of diterpenes. For instance, the
amphilectane skeleton of the pseudopterosins, and the biosynthetically related serrulatane framework of the seco-pseudopterosins, have only been reported from one species,
P. elisabethae. Further, dolabellane diterpenes are restricted to
the genus Eunicea, pseudopteranes are restricted to the genus
Pseudopterogorgia, and xenicane diterpenes have only been
reported from Acalycigorgi inermis. The organisms described in
this review belong to the order Gorgonacea and are representatives of three suborders, Scleraxonia, Holaxonia and Calcaxonia.
As is evident from Fig. 4, the diterpene chemistry of the Scleraxonia is dominated by briaranes and the closely related cladiellanes.
With the exception of two compounds from Plumarella sp.,
gorgonians of the suborder Calcaxonia only produce diterpenes of
the briarane class. While briaranes are common in the suborders
Scleraxonia and Calcaxonia, members of the Holaxonia do not
contain briaranes but rather contain terpenes with cembrane and
geranylgeranane skeletons. Thus, there appear to be some key
differences in the classes of terpene skeletons at the suborder level,
and progressively less at the levels of family and genus.
A report by Dorta and co-workers suggests that the oxidation
of C-18 of furanocembranolides may be useful as a chemotaxonomic marker for several genera of octocorals,71 and this review
suggests that diterpene chemistry may be of use in certain cases in
assisting with taxonomic assignments at the levels of suborder,
family and possibly genus. To further develop the classification
of gorgonians, various molecular methods are now being used
for taxonomic purposes, and such approaches have recently been
applied to understand relationships within the family Plexauridae.189 It therefore appears that a combination of molecular,
chemical and classical morphological analysis should be used
Fig. 4 Classification of carbon skeletal types (amphilactane, briarane, cembrane, cladiellane, dolabellane, gerenylgeranane, pseudopterane, serrulatane
and xenicane) by genus of gorgonian. A total of 592 diterpenes have been reported from gorgonians in the period 1995 to April 2008. Numbers in
parentheses indicate the total number of terpenes isolated from the associated phylogenetic groups and skeletal classes.
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Fig. 5 Incidence of diterpene classes from Pseudopterogorgia spp.
collectively. Further, it should be noted that terpene biosynthesis

has been shown to proceed in the absence of the gorgonian in two
separate cases.109,110 If it is demonstrated that this is a general
phenomenon, the nature and specificity of the relationship
between the microbe and the gorgonian host could prove to be
intriguing questions in the next few years.
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Diterpenes from gorgonian corals

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Covering: 1995 to April 2008

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three suborders: Scleraxonia, Holaxonia and Calcaxonia (Fig. 1).

2.1 Family Anthothelidae

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relative configurations of these metabolites were elucidated by

the briarane [erythrolides RU (2023)], erythrane [erythrolide

Russell Kerr received his B.Sc.

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Fig. 1 Cladogram of the order Gorgonacea.

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2.2 Family Briareidae

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The isolation and the structure determination of briareolate

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AM (6173) and excavatolides UZ (7479) were isolated from

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wide range of cytotoxicity toward P-138, KB, A-549 and H-19

Nat. Prod. Rep., 2009, 26, 681710 | 685

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This journal is The Royal Society of Chemistry 2009

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This journal is The Royal Society of Chemistry 2009

respectively.41 Analysis of an Indonesian Briareum sp. has led to

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This journal is The Royal Society of Chemistry 2009

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elucidated by spectroscopic analysis supported by X-ray data.50

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690 | Nat. Prod. Rep., 2009, 26, 681710

This journal is The Royal Society of Chemistry 2009

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(274276), were isolated from Eunicella labiata collected off the

This journal is The Royal Society of Chemistry 2009

diterpenoids belonging to the eunicellane class (280282),64

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Lophogorgia peruana. An investigation of Lophogorgia peruana

692 | Nat. Prod. Rep., 2009, 26, 681710

structurally complex and biological significant metabolites.1,75

This journal is The Royal Society of Chemistry 2009

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spectral comparisons with known pseudopterane and cembrane