: A ‘ Hot Spot’ for Valuable Chemodiversity : Part 2: Basal Angiosperms and Eudicot Paul Coulerie, Cyril Poullain

To cite this version:

Paul Coulerie, Cyril Poullain. New Caledonia: A ‘ Hot Spot’ for Valuable Chemodiversity : Part 2: Basal Angiosperms and Eudicot Rosids. Chemistry and Biodiversity, Wiley, 2016, 13 (1), pp.18 - 36. ￿10.1002/cbdv.201400389￿. ￿hal-01937774￿

HAL Id: hal-01937774 https://hal.umontpellier.fr/hal-01937774 Submitted on 23 Feb 2021

HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. NewCaledonia:AHot Spotfor Valuable Chemodiversity

Part 2: Basal Angiosperms and Eudicot Rosids

by Paul Coulerie*a)b)and Cyril Poullainc)d) a)Institut Agronomique nØo-CalØdonien,Connaissance et AmØlioration des Agrosyst›mes,BPA5, 98848 Noumea Cedex, New Caledonia b)School of Pharmaceutical Sciences,University of Geneva, 30, Quai Ernest-Ansermet, CH-1211 Geneva 4 (phone: 41-22-3793409; e-mail:[email protected]) þ c)Centre de Recherche de Gif,Institut de Chimie des Substances Naturelles,CNRS,Labex LERMIT,1Avenue de la Terrasse, FR-91198 Gif-sur-YvetteCedex d)Stratoz, 5, Rue de la Baume,FR-75008 Paris

Theflora of New Caledonia encompasses more than 3000 species and almost80% are endemic. New Caledonia is considered as ahot spot for biodiversity.With the current global loss of biodiversityand the fact that severaldrugs and pesticides becomeobsolete,there is an urgentneed to increasesampling and research on new natural products.Inthis context,wereview the chemical knowledge available on New Caledonian native flora from economicalperspectives.Weexpect that abetter knowledgeofthe economic potential of plant chemistry will encourage the plantation of native for the development of a sustainable economy which will participate in the conservation of biodiversity.Inthe second part of this review,wefocus on the results exposed in 60 scientific articlesand describe the identification of 225 original compounds from basal angiosperms and eudicotrosids.Wediscuss the economic potential of plants and molecules from medicinal and industrial perspectives.This review also highlights severalplants and groups,such as Amborella sp., Piperaceae,orPhyllanthaceae,that are unexplored in New Caledonia despite their high chemical interest. Those plants are consideredtohave priority in future chemical investigations.

Introduction. –The importance of biodiversity for the New Caledonia, an archipelago locatedinthe South- discovery of new naturalproducts with economicalvalue West Pacific, is considered as one of the 34 majorhot spots was recognized in 1990 duringameetingofthe Interna- for marine and terrestrial biodiversity [7]. Areview tional Society of Chemical Ecology.Inthe Gçteborg published in 2004 by Laurent and Pietra highlighted the Resolution [1],natural product diversity was recognized pharmacological potential of the Neo-Caledonian marine as atreasuryofimmense value to human kind. This organisms [8], but no review of terrestrial phytochemical resolution also pointed out the currentalarming rate of investigationsisavailable yet. Considering higher plants,it species extinction that is rapidly depleting this treasury, is evaluatedthat New Caledonia contains3270 native with potentially disastrous consequences.This encouraged species,ofwhich 78% are endemictothis territory [9].This the research for valuable naturalproducts for the valor- botanical diversityalso represents ahuge reserve of ization and protectionofbiodiversity [1].From time original naturalcompounds and providesareal interest immemorial, plants have provided awide variety of foods, for green chemistry,pharmacology,cosmetics,and agrono- drugs,cosmetics,fibers, and building materials,and have my.The term hot spot also points out that the biodiversity been fundamental for the development of human societies is highly threatened by human activities and therefore, this [2]. Morerecently,studiesofplant chemistry have led to habitat must be protected [10]. Forthis purpose,the the discovery of many bioactiveproducts,such as for discovery of interesting chemicals from plantswill encour- pharmacological,agronomical, or cosmetic applications. age the reforestation and thus,the protection of biodiver- Thediscovery of aspirin from Filipendula ulmaria or of sity.Investigations of the New Caledonian chemodiversity artemisinin from Artemisia annua are among the most already provided original compounds and/or interesting popularexamples that illustrate the importance of such drugs.Asanexample,methoxyellipticine, an alkaloid research [3][4].Despite the development of combinatorial found in aNew Caledonian Apocynaceae,was used to chemistry and rational drug design,many authors argue develop adrug (Celiptium)used to treat breast and liver that natural products are likely to continuetoprovidethe cancers [11]. best lead-moleculesinthe future [5][6].Inthis context, Despite phytochemicalinterest, plant chemistry re- species-rich areas,such as tropical and subtropical forests, mains largely unexplored in New Caledonia. During the are of particular interest. second part of the 20th century, research mainlyfocused on the discovery of original compounds (e.g.,[12 –14]). Later, the published phytochemicalstudies on New Caledonian biological evaluations started to be systematically associ- angiosperms led to the isolationoforiginal naturalcom- ated to phytochemical analysis (e.g.,[15 –17]).This was the pounds.Also,severalofthem wereshown to be highly beginning of research for economical evaluation, in a bioactive,showing high potential for pharmaceutical ap- purpose of biodiversity conservation. Following the review plications. On the contrary,other economic perspectives of isolated alkaloids from New Caledonian flora by SØvenet for New Caledonian plants, such as cosmetic or agronomic and Pusset [18], we present here abroaderreview of the applications,are poorly documented. As summarized in phytochemistryofNew Caledonianplants and discuss their Fig. 1,wecan also notify that we did not find any economic potential. This review summarizespublications publication related to endemic speciesfrom 60% of the available on SciFinder from 1972, when the first formal angiosperm families. phytochemical studies of endemic plants were published, up to early 2015. Protoangiosperms, Monocots, and Basal . – Theknowledge availableinscientific literature about Annonaceae. This family is represented by twelve species the chemistry of New Caledonian native plants is reported (includingelevenendemic species)that are divided into six exhaustively.The data are organized by families of plants, genera. Annonaceae is ahuge tropicalbotanicalfamily that according to the phylogeny proposed by the Angiosperm encompasses more than 2000 species including several Phylogeny Group III (APG III;see Fig. 1)[19].This allows comestible fruits (e.g., Annonasquamosa and Annona acomprehensive chemotaxonomicalorganizationofthis muricata)orplants used for perfumery (e.g., Cananga review.Floricalwas used as taxonomical reference for the odorata and Mkilua fragrans). Annonaceae are known to New Caledonian flora [9]. This review points out the contain polyphenols (includingunusualC-benzylflavo- economic interest of terrestrial biodiversity of New Cale- noids), terpenes, acetogenins,and alkaloids (mainly from donia and highlights new groups which have been poorly the isoquinolinegroup)asshown in many publications studied and may contain novel compounds.This compila- dedicatedtothese plants (e.g.,[22]and [23]).They are also tion highlights that the original flora from New Caledonia frequently describedinfolk medicines [24]and numerous also contains awide range of original compounds.Origi- species show strong bioactivities,such as insecticidal or nality of New Caledonian compounds was updatedusing antitumoral activities[25][26]. the Dictionary of Natural Products [20]. We considered Thechemistry of five species has beeninvestigated in compounds as originals when encounteredonly in a New Caledonia: Xylopia pancheri, Xylopia vieillardii, restricted number of endemicspecies stemming from a Meiogyne tiebaghiensis (syn.: Desmos tiebaghiensis), Hu- unique .1)Wealso point out that alot of work bera nitidissima (syn.: Polyalthia nitidissima), and Gonio- remains to be done for the development of economical thalamus dumontetii.Thirteen isoquinolinealkaloids,in- applications based on this biodiversity.This review is cluding an unusual morphinanedienone (pallidine;shown divided into three parts.The first part coversthe knowl- in Fig.2)were identified from M. tiebaghiensis [18].X. edge of the chemistry of New Caledonianconifers[21], pancheri and H. nitidissima containagreat variety of whereas the two followingparts focus on the metabolites aporphine and isoquinolinealkaloids from benzylisoquino- isolated from angiosperms.The secondpart, which is line and protoberberine groups, including four lindoldh- presented here,compiles the results obtained by investiga- aminederivatives (namely N,N-dimethyllindoldhamine*, tion of basal angiosperms,monocots,basal eudicots,and isodaurisoline*, 7-O-methyllindoldhamine*, and 7’-O- eudicot rosids. methyllindoldhamine*) that are presented in Fig.2 [18] In NewCaledonia, angiosperms are particularly diverse [27][28]. Only few biological tests were associated to those sincethis groupencompasses 3099 species, more than 90% studies despite that several classicaldrugs,such as mor- of all vascular plants,and is characterized by its remarkable phine,possess an isoquinolineskeleton. Indeed, only X. originality,showing 77.8% endemism[9].More in detail, pancheri demonstrated light periphericalvasodilatory several groups whichare abundantly representedinthe activity [18]. tropics are totally absent in New Caledonia, such as H. nitidissima also contains several flavonoids,such as Balsaminaceae and Begoniaceae,and other groups, such mangiferin (see Fig.3)and quercetin derivatives. of as Annonaceae,Asteraceae,orBignoniaceae,are clearly this plant contain ahigh concentration of mangiferin and under-represented [9]. In parallel,wecan find several are considered as an important natural source for this relictual taxa, Amborella trichopoda being the perfect natural colorantand powerful antioxidant [29]. G. dumon- example,and ahigh levelofspeciation in several gondwa- tetii was also investigatedfor protein kinase inhibition nian groups,such as Lauraceae (47 endemic species)or activity (DYRK1A and CDK1/cyclin B) for anticancer (90endemic species,corresponding to 30% of perspectives or neurodegenerative treatment. It contains the world diversity of this group)[9]. and aristolactams (namely velutinam, aristolactams AII and Rubiaceae are the most important families,encompassing AIIIa)and one lignancalled( )-medioresinol (see Fig. 3). 257 and 211 species,respectively.Aswill be shown, many of Aristolactam AIIIa (see Fig.2À )isastrong inhibitor of

DYRK1A and CDK1/cyclin Bshowing IC50 values of 1)Original compounds are tagged by an asterisk in the text and 0.08 and 0.2 mm on these enzymes [30][31].Despite figures. strongevidencefor the possible economicalpotential Fig. 1. Phylogenetic of New Caledonian basalangiosperms and eudicot rosids realized with TreeGraphand data from APGIII (see the Supporting Information2)for the entire phylogenetic tree of New Caledonianplant families).Chemical families encoutered in endemic species are mentioned on the right. EO,essential oil. 0Correspondstocomplete absence of chemical knowledge for any endemicspecies of afamily (nothing is mentionedfor families containing no endemic species). Fig. 2. Structuresoforiginal and bioactivecompounds isolated from Annonaceae

Fig. 3. Remarkable polyphenols isolated from Annonaceae

Fig. 4. Examples of alkaloids isolated from Atherospermathaceae of this family,especially for drug discovery and cosmetics, as chalcones or flavanones,and to biosynthesize alkaloids, the knowledge concerning the chemistryofNew Caledo- mainly belonging to the isoquinoline group.Bisbenzyliso- nian Annonaceae is scarceand should be further quinolines are evenconsidered as chemical markers of this studied.2) family [20]. Barks and leaves of N. vieillardii were Atherospermaceae.Nemuaron is amonospecific genus investigated for their alkaloidal content. Consistent with and Nemuaron vieillardii is the only memberofthe family the chemotaxonomic knowledge presented above,this Atherospermaceae in New Caledonia. This tree is foundin study revealed the presenceofnumerousisoquinoline humid forests of the main island.Elsewhere in the world, alkaloids, suchaslaurotetanine, norisocorydine,atheroline, this family is known to produce phenolic compounds,such and nemuarine*, an originalbisbenzylisoquinoline [18]. Thestructuresofthese alkaloidsare presented in Fig.4. 2)Supportingmaterialisavailable upon request from the authors. N. vieillardii also produces anise smelling aromatic com- pounds.Thus,the plantisapotential sourceofessential oils violacea), an important pest for crop fields [37].A and could be of interestfor the perfume industry. However, preliminary investigation of volatiles fromthis plant did according to our knowledge,noanalysis of the essential oil not allow us to explain this biological activity. contentofthis plant has been reported yet. Lauraceae. ThefamilyLauraceae is represented in New Hernandiaceae. This family is representedinNew Caledonia by six genera (including the endemic genus Caledonia by two genera and three species,includingthe Adenodaphne)and 48 species,all beingendemic except endemic plant Hernandia cordigera. Species from this Cassythafiliformis.Lauraceae is an important tropical and family,including Gyrocarpus americanus which is native to subtropicalfamily in terms of diversity,comprising 30 to 50 New Caledonia, are described to contain lignans and genera and ca. 2000 species, but also from an economical alkaloids [32][33]. H. cordigera also produces several point of view,since it contains important species exploited characteristic lignans,such as 5’-methoxyyatein*, 5’-me- for timber(e.g., Ocotea bullata), food (e.g., Persea amer- thoxypodorhizol, and cubebininolide, that are presented in icana), or fragrances(e.g., Aniba rosaeodora). Phytochem- Fig. 5,and aporphine alkaloids(e.g.,cassythicine, nandi- icals in Lauraceae are diverse and include alkaloids(e.g., gerine,nantenine, hernagine,and ogiverinewhich are benzylisoquinoline and aporphine derivatives), essential presented in Fig.6)[18]. oils,polyphenols,and terpenoids [20][38]. Hernandia nymphaeifolia (ex Hernandia peltata)also New CaledonianLauraceae werefirst investigated for contains alkaloids includingaporphine derivatives,togeth- their alkaloidal content (seeoriginal structures in Fig. 7). er with furanoid lignans whichshowed potent antiplatelet In 1985, Tillequin, Koch et al. described the presenceoftwo aggregation activities and could potentially be used as new morphinane alkaloids with asaturated C-ring (oreo- naturalanticoagulants in the future [34].Further biological beiline* and6-epioreobeiline*)togetherwithknown alka- evaluation should be encouraged by the fact that aporphine loids(wilsonirine, thaliporphine, isoboldine,and pallidine) alkaloids and lignans, such as the antiprotozoal agent in Beilschmiediaoreophila [39].Among the19endemic lysicamine [35] or the anticancer agent aviculin [36],can Cryptocarya speciesthatare referenced in NewCaledonia, be highly active natural compounds. Otherwise,the heart five specieswereinvestigatedfor theirchemicalcontent. wood of H. cordigera has been exploitedinthe past for Bioguided fractionation of aleaf extract of Cryptocarya carpentry and is also traditionally used in New Caledonia chartacea led to the isolation of pinocembrin and six new for attractingand trapping chrysomelids(Monolepta semi- mono- and dialkylated flavanones named chartaceones

Fig. 5. Lignans isolated from H. cordigera

Fig. 6. Examples of alkaloidsisolated from Hernandiaceae Fig. 7. Original alkaloids isolatedfrom Lauraceae

Fig. 8. Original flavonoidsisolated from C. chartacea

A* –F*(see Fig. 8). Chartaceones C* –F*show strong velutinosa [18]. Thecytotoxic activities of some of these inhibitory activitiesonthe dengue virus RNApolymerase, compounds were evaluated against KB cells andrevealeda with IC50 values ranging from 1.8to4.2 mm,and thus could significant anticancer potential of antofine derivatives, lead to the discovery of anew antiviral drug [40]. whichdisplayed IC50 values ranging from 1to6.3 nm Cryptocarya longifolia, Cryptocarya odorata,and Cryp- [18][41].Otherwise,essentialoil obtainedfrom the wood tocarya oubatchensis containmany isoquinoline alkaloids, of Cryptocarya odorata was also studied and was charac- such as antofine,laurotetanine, and laurolitsine,and terized by the presence of uncommon a-pyrone derivatives, original structures,such as longifolidine*and longifolo- such as 6-heptyl-5,6-dihydro-2H-pyran-2-one[18]. nine* (see Fig. 7), which were isolated from C. longifolia Twoofthe 14 endemic Litsea species were also [18]. Thus, C. oubatchensis contains two original seco- investigated.Aporphinoid alkaloids, tetrahydroisoquino- dibenzopyrrocoline alkaloids called cryptowolinol* and line,and an orphinane dienone alkaloidwere isolated from cryptaustoline* (see Fig. 7).Cryptocaryaphyllostemon also the leaves of Litsealecardii. Corydine, glaucine,and N- was characterized by the presenceofcryptowoline*, methylcoclaurine were isolated from the leaves of Litsea phyllostemine*, phyllosteminine*, phyllosterone,phylloc- triflora and were later found in other plant families as well ryptine*, and phyllocryptonine* (see Fig. 7)[18]. Velu- [18]. Other endemic Lauraceae have not been investigated cryptine*(see Fig. 7)was isolated from Cryptocarya yet. Moreover, an extended evaluationofbioactivities of Fig. 9. Typical alkaloids encountered in Menispermaceae these plants may lead to the discovery of new naturaldrugs in view of the alkaloidal content of these plants.Also,some speciesare highly aromatic and should be studied for cosmetic perspectives. Menispermaceae. Menispermaceae are represented in New Caledonia by seven species (five endemic)and are dividedinto four genera.Among the endemic species, only Fig. 10. Originalalkaloid isolated from H. baudouini Pachygone loyaltiensis (ex Pachygone vieillardii)has been investigated. This plant is describedaspurgative in Melanesian traditionalpharmacopoeia. It is characterized investigated recently due to its anticancer potential [44]. by dimeric alkaloids,such as daphnoline and daphnandrine Abioguided fractionationofthis plant extract was (see Fig.9), together with other alkaloids that have not performed to find new compounds with anticancer or been identified yet [18]. Otherwise,anoriginal alkaloid antineurodegenerative potential. This studyled to the called hypserpine* (see Fig. 9)was isolated from the bark isolation of six phenanthrene derivatives,includingtwo of Hypserpa neocaledonica.Finally,the chemistry of novel derivatives,namely 2,3,5,6-tetramethoxyphenan- Stephania japonica has been investigated, mostly for threne-1,7-diol and blestrin E(see Fig. 11). Themost alkaloids of different groups (e.g.,aknadicineand proto- activecompounds,2,3,5,6-tetramethoxyphenanthrene-1,7- stephanine which are shown in Fig.9)and for several diol and 3,4,6-trimethoxyphenanthrene-2,7-diol (see bioactivities,such as antimicrobial and multidrug resistance Fig. 11), exhibited IC50 values of 0.07 and 0.2 mm on reversing activities [42]. CDK1/cyclin B, respectively [44]. Orchidaceaecomprises Monimiaceae. This family is represented in New more than 200 species and half of them are endemic to New Caledonia by ten endemic species: Kibaropsis caledonica, Caledonia. All of theseplants are strictly protected and the only memberofthis genus,and nine Hedycarya species. their chemical investigation should be associated with Other members of this family are knowntocontain horticulturalmultiplication to be considered. essentialoil and variousoriginal and/orbioactive chem- Proteaceae. Proteaceae is an important tropical and icals,such as alkaloids and butanolides [43]. In New subtropical family.Itcontains ca. 2000 species that are Caledonia, only Hedycarya baudouinii was investigated by mostly concentratedinthe southern hemisphere.InNew phytochemists.Itcontains awide rangeofalkaloids, Caledonia, it is representedby43endemic species, includingisoquinoline,pavine,and aporphine derivatives classifiedinto nine genera. Only few species have been includingthe original compoundhedycarine* which is investigated for theirchemical content or economical shown in Fig.10 [18]. Other Monimiaceae should be potential. Eleven original tropane alkaloids were isolated investigated,atleast for their alkaloidal content and to from leaves of Eucarpha strobilina (ex Knightia strobilina): search for new bioactive compounds. acetylknightinol*, strobiline*, dihydrostrobiline*,knighto- Monocots. Among all studies on monocots (more than line*, knightinol*, 3a-(cinnamoyloxy)tropan-6-ol*, 6b- 500 species and 48% endemism)wecould not find any (benzoyloxy)-3a-hydroxytropane (also found in Erythrox- publication dealing with the chemistry of an endemic ylum spp.),strobamine*, chalcostrobamine*, strobola- species from New Caledonia. Indeed, the chemistry of mine*, knightalbinol*, and knightolamine* [13][45]. Two Appendicula reflexa,anative Orchidaceae,has been examplesofthesestructuresare given in Fig. 12. Fig. 11. Originaland bioactivephenanthrene derivatives encountered in anative Orchidaceaespecies

Other members of this family,such as from the endemic genera Beaupreopsis, Garnieria, Sleumerodendron,and Virotia,are still untouched. Recently, fatty acids from seeds of Grevillea exul var. rubiginosa and Alphitonia neocaledonica (Rhamnaceae)have been investigated. They are characterized by ahigh percentage of unsaturated Fig. 12. Typical original tropane alkaloids encountered in endemic fattyacids and are even considered by the authors as a Proteaceae promising sourceofw-5-monoenes that are uncommonin the plant kingdom [48]. As shown in this article,the Other related original tropanealkaloids were also investigation of the nutritive potential of seeds is also an isolated from leaves of Eucarpha deplanchei (ex Knightia original axis for the research of economical valorization of deplanchei): 2-benzyltropane-3,6-diol*, O-acetyl-2-benzyl- the New Caledonian flora. It could be extended to other tropanol*, 3-O-benzoyl-2-benzyltropanol*, 6-(benzoyl- families.Finally, Grevillea spp., Beauprea spp., Virotia spp., oxy)-2-(hydroxybenzyl)tropan-3-ol*, and 6-(benzoyloxy)- and Stenocarpus milnei are under investigation by Stratoz 3-(cinnamoyloxy)-2-(hydroxybenzyl)tropane* [18]. Origi- SAS and local research centersfor theircontentof nal cyclophanes from the turrianegroup were isolated from manganese binderswith industrial application in catalysis Kermadeciaelliptica: kermadecins A* –H*[46]. Kerma- for green chemistry.These investigationsare closely decins I* and J* and isokermadecins D* and F* were associated with revegetalization programsofdamaged sites isolated from the bark of Kermadecia rotundifolia [47]. after mining. Kermadecins A* and B* (see Fig. 13)showed significant Winteraceae.Zygogynum is the only genus of this anticancer activities againstL1210 and KB cells [46], while family that is present in New Caledonia. It comprises 31 kermadecins D* and F* and isokermadecin D* (see endemic species. SØvenet and Pusset revealed the uncom- Fig. 13)possess significant inhibitory effects on acetylcho- mon alkaloidal contentofZygogynum pauciflorum [18]. linesterase [47]. They isolated the original alkaloids calledbubbialine* and

Fig. 13. Examples of bioactive original cyclophanes isolated from Kermadecia spp. 9-enoate (2), 3-[(7Z)-hexadec-7-en-1-yl]-4-hydroxy-5-me- thoxy-5-methylfuran-2(5H)-one (3), which are shown in Fig. 16,together with twelve drimane sesquiterpenes (six new structures including the two examples shown in Fig. 17)from Z. pancheri and Z. acsmithii [50].Two original drimanes,namely isodrimanial* and 1b-{[(E)-4- Fig. 14. Original alkaloids isolatedfrom Winteraceae methoxycinnamoyl]oxy}bemadienolide*(Fig.17)were al- so isolated from the bark of Z. baillonii [51]. Drimanesendowedwith adialdehydefunctionality, bubbialidine* (see Fig.14)which are structurally related to such as isodrimanial* that is shown in Fig. 17,showed nor-securinine,acompound that was previously isolated potent cytotoxic activities againstKB, HL60,and HCT116 from . cancer cells (IC50 values ca. 1 mm)[51]. Other phytochemical studies led to the isolation of four original and bioactivetetralones,namely zygolone A*, 4’- Eudicot Rosids. Fabiids. Calophyllaceae. This family O-methylzygolone A*, 3’-deoxyzygolone A*, and isozygo- consists of four speciesinNew Caledonia, half of them lone A* (see Fig.15), from Zygogynum stipitatum, Zygo- being endemic,and comprisestwo genera. Pantropical gynum pancheri, Zygogynum acsmithii,and Zygogynum Calophyllum inophyllum (tamanou)has been widely baillonii [49]. These compounds expressedpotentbinding studied, especially for the oil obtained from its seeds which activities on peroxisome proliferator-activated receptor-g proved to be vulneraryand cicatrizing. Calophyllolide, and thus could be potentially used for treatment of inophyllum, and other complex polyphenols are considered diabetes.Tetralones also showed cytotoxic activities against as responsible for such effects [52].Moreover, inophyllums

KB cancer cells with IC50 values ranging from 1.4to6.5 mm showed inhibition of HIV-1 reverse transcriptase in cellulo, [49]. with IC50 values ranging from 1.4to1.6 mm [53]. In asecond study, Allouche et al. isolated three addi- Otherwise, Calophyllumcaledonicum contains charac- tional original butanolides,(3S,4R,5S)-3-[(7Z)-hexadec-7- teristic calolongic acid and caledonic acid* together with en-1-yl]dihydro-4-hydroxy-5-methylfuran-2(3H)-one (1), twelve original xanthones,such as caledonixanthones A* – methyl(2S,9Z)-2-[(1R)-1-hydroxy-2-oxopropyl]octadec- M* (see Fig. 18)[54 –56].The latter compounds displayed

Fig. 15. Original zygolone derivatives identified in Winteraceae

Fig. 16. Original butanolide derivativesidentified in Winteraceae Fig. 17. Originalbioactive drimane sesquiterpenes isolated from Winteraceae

Fig. 18. Examples of acids and original xanthones encountered in Calophyllaceae antifungal and antimalarial activities [56][57].Itcould be oil content [60]. Most of the New Caledonian members of also interesting to investigate the coumarincontentof this family remain totally unexplored. In view of the results endemic Calophyllaceae,since they have been previously obtains previously, represent an attractive identified in this family and are frequently describedto groupfor the discovery of new bioactive compounds. exhibitpharmacological and cosmetic potential [58][59]. Clusiaceae (ex Guttiferae). This family is represented Celastraceae. This family is represented by 24 species, in New Caledonia by 20 species and is divided into two including 21 endemics, and comprises seven genera (in- genera (Garcinia and the endemic genus Montrouziera). cludingthree endemics). Despite the originality of New SomeClusiaceae are majestic ,such as Montrouziera Caledonian Celastraceae,only two endemicspecies have cauliflora,and can be used for joinery work. From a been investigatedfor theiralkaloidalcontent yet. Peripter- chemical point of view,four of the 14 endemic Garcinia ygia marginata containsoriginal cinnamoylspermidine species were shown to contain xanthones that are related to derivatives (namely periphylline*, dihydroperiphylline*, various biological activities,such as antimalarial and isoperiphylline*, and neoperiphylline*) and Dicarpellum antileishmanial activities [56][60 –64].Examples of orig- pronyensis contains a-aminoalcohols togetherwith uncom- inal and bioactive xanthones are given in Fig.20. mon linearsympathomimetic alkaloidscalled dicarprines Five new depsidones (garcinisidones B* –F*) were A* –C*[18]. Examples of thesestructures are presented in isolated from Garcinia neglecta and Garcinia puat (var. Fig. 19. puat). These compounds expressed antiviral activities Also, paniculatus,atraditional ayurvedic against the Epstein –Barr virus and potential for cancer medicinal plantused because of its various neuroactive chemoprevention [61]. Garcinia vieillardii also contained properties (e.g.,memoryenhancing, analgesic, and sedative numerous xanthones,such as pancixanthones Aand B, properties)has been studied, especially with regard to its isocudraniaxanthones Aand B, original vieillardiixan-

Fig. 19. Original and unusual alkaloids encountered in Celastraceae Fig. 20. Examples of original xanthones isolated from Garcinia spp. thones A* –C*(see Fig.20), and 5,6-di-O-methyl-2-dep- with b-and d-tocotrienol, and benzophenones,such as renylrheediaxanthone*, together with two benzophenones, cotoin [64][65]. Anotherstudy focused on tocotrienol namely clusiachromene and 3-geranyl-2,4,6-trihydroxyben- derivatives from Garcinia amplexicaulis and confirmed the zophenone [57][62][63]. great interest in this genus fromcosmetic perspectives due Garcinia virgata,which has been studied out of to antiangiogenic activity [66]. Finally,anew xanthone cosmetic interest, containsvarious xanthones,including calledmontrouxanthone* and adihydroisocoumarin, mon- the novel virgataxanthones A* and B* and the cytotoxic troumarin* (see Fig. 20), along with the two known anti-KB guttiferones Iand J* (see Fig. 20). It also produces compounds 1,3,5-trihydroxy-4-(3,7-dimethylocta-2,6-dien- original formylated tocotrienols* (see Fig.21), together 1-yl)-9H-xanthen-9-one and kaerophyllin, were isolated from Montrouziera sphaeroidea [67]. Other Montrouziera species have not been investigatedyet. Cunoniaceae. Despitethe wide diversityand originality of the CunoniaceaeinNew Caledonia,only little is known about the chemistry of these plants.This family is representedby90species,all beingendemic, and comprises four genera (including two endemicgenera: Codia and Pancheria). Fogliani and co-workers studied various bio- logical activities of 50 Cunoniaceae crude extracts,such as antimicrobial, anti-inflammatory,orantidiabeticalactivi- ties,searching for inhibitors of xanthine oxidase and scavengers of superoxide anions.They demonstrated the presence of ellagitannins (ellagic acid 4-O-b-d-xylopyrano- Fig. 21. Original and bioactivetocotrienolderivatives isolatedfrom side,mallorepanin,and mallotinic acid along with corilagin, Clusiaceae chebulagic acid, ellagic acid, and gallic acid)with anti- microbial activityinCunonia macrophylla [68 –70].Fur- Also, Macaranga vedeliana has been studied by ethno- ther investigations are necessary to find out whether the pharmacologists.This plant is used by traditional Kanak local unusual botanicaldiversityofthis group (30% of healers to relieve pain and cure tonsillitis.Chemical Cunoniaceaespecies beingendemic to New Caledonia)is investigationsofthe leaves of M. vedeliana led to the related to an original chemical composition. discovery of macarangin, ageranyl-substituted flavonol, Euphorbiaceae. This family is highly represented in and vedelianine,ahexahydroxanthene derivative,that New Caledonia:19genera that consist of 72 species (58 have been found later in other Macaranga spp.[73][74]. endemics). Other Euphorbiaceae are also of high econom- Other pantropical specieshave been studied, for example ic importancethroughout the world. Indeed, their chemical Excoecaria agallocha,which contains numerous original investigation led to the discovery of many active com- terpenoids, such as seco-labdane diterpenes of the excoe- pounds and several of them,such as prostratin and carin series and phorbolesters (e.g.,[75]and [76]). jatrophane,are now commercializedasdrugs [71].To Otherwise,the bioguidedfractionation of bark extracts assess their important pharmacological potential, we from Trigonostemon cherrieri led to the isolation of should mention that Euphorbiaceae speciesare oftencited antiviral O-bearing daphnane diterpenoidorthoesters with by traditionalhealers in New Caledonia as in other an uncommonchlorinated moiety:trigocherrins A* –F* countries [24]. and trigocherriolides A* –D*[77][78]. Examples of these However, only few species were chemically investigat- compounds are presented in Fig.22.These results confirm ed:the genus Croton is frequently described in the the interest in terpenoids from Euphorbiaceae,especially literature as arich source of biologically active compounds, for the search of antiviral compounds [71].Other species, such as compounds showingantiulcer, antitumor,and co- such as Homalanthus spp., that are described in the carcinogenic activities. In New Caledonia,this genus is traditional Kanakpharmacopoeia proved to be active in representedbytwo species, and one of them has been preliminary biological screening and should be subjected to investigated. Several original diterpenes,includingthe new further investigations. trachylobanes crotinsularinand crotinsulactone,and the Chemical investigationsofEuphorbiaceae can also be new clerodane-typeterpenoids furocrotinsulolides Aand oriented towardother goals. peltatum and B, and anew phenolic disaccharide (3,4-dimethoxyphenyl pancheri are known to be strongly refused by rutinoside)were isolated from the non-endemic species herbivorous animals.AchemicalinvestigationofF. pan- Croton insularis [72].The structures are shown in Fig. 22. cheri led to the identification of anew guanidine-type

Fig. 22. Examples of significant bioactive and original terpenoidsencountered in Euphorbiaceae alkaloid:fontaineine [79].This indication may lead to the discovery of other interesting toxic compounds in C. peltatum.The family Euphorbiaceae also contains aromatic plants which could be investigated for potential use in perfumery (e.g.,flowersofBaloghia spp.). Cocconerion balansae,famousinNew Caledoniafor its bloody sap,may containflavonoids or coumarins but no scientific publica- tion is available concerning this plant.Weare convinced that this group shouldbefurther investigated due to Fig. 25. Alkaloids isolated from cosmetic and pharmacological potential. . This family is represented in New Caledonia by six Hugonia species,all but one being endemic.Absou- were isolated from the leaves of this plant (see structures in line*, an original alkaloid presented in Fig. 23,and four Fig. 25): homaline,hopromine*, hopromalinol*, and ho- other pyrrolizidin alkaloidswere isolated from Hugonia prominol* [18]. oreogena and Hugonia penicillanthemum [18]. Pyrrolizidin Other members of this family may contain original and/ alkaloidsmight be synthetized by plants to protect or bioactive compounds.Wethink that this groupshould themselves against herbivores and were frequently report- receive moreattentionfrom phytochemists,especially the ed to be responsible for planttoxicity [80]. endemic Lasiochlamys genus that containseleven species. Casearia silvana, Lasiochlamys peltata,and Xylosma vin- centii were studied for their Ni content [81];these species synthetize specialbinders of Ni, such as acitrate-complex form [82].These organometallic complexes are of high interest since they are used to improve the yield and stereoselectivity of chemical synthesis [83]. Violaceae. This family is representedinNew Caledonia by nine species,all being endemic, and is divided into two Fig. 23. Original alkaloid found in Hugonia spp. genera.Only one species was studied: Hybanthus austro- caledonicus.Anew hopane-type triterpenoid, 3-epiwood- . Rhizophoraceaeisrepresented in wardinic acid* (see Fig.26)together with otherpreviously New Caledonia by twelve species (five endemic) and is isolated compounds,such as 24-methylidene cycloarte- divided into four genera. These plants comprise the none,24-methylidene cycloartenol, b-sitostanone,21b- mangroves and thus,are restricted to an extreme environ- hydroxycaloncobalactone,and daucosterol, were isolated ment. Theparticular edaphic conditions related to Rhizo- from the extract of this plant [84]. phoraceae could also affect their chemical composition. Moreover, H. austrocaledonicus is knownashyper Among the five endemic species that are listed in New Ni-accumulating species and shown to contain several Caledonia, three of them belong to the genus Crossostylis: metabolites synthetized especially for heavy metal chela- Crossostylis biflora, Crossostylismultiflora,and Crossosty- tion [85]. lis sebertii.Each of them contains alkaloids, such as hygrine Malvids. Meliaceae. This family is represented in New and tropanol derivatives,including the uncommon disulf- Caledonia by 13 species,including eight endemics,and is urated brugine (see Fig.24), an alkaloid that has been divided into fourgenera. Two Dysoxylum spp.have been found only in Rhizophoraceae [18]. To the best of our studied and both contain bioactive terpenoids. Dysoxylum knowledge,noother species have been investigated macranthum contains eleven original tirucallane-type tri- regarding their chemicalcontent. terpenes, dymacrinsA*–K*(see examplesinFig.27), Salicaceae (ex ). Salicaceae are repre- together with two previously described tetracyclic triter- sented in New Caledonia by 56 species,all but one being penes and two known pregnane steroids [86].Dymacrins endemic, and are divided into four genera. Homalium B*,C*, H*, and J* showed moderate cytotoxic activities 1 encompasses 18 species and one of them, Homalium against KB cells (IC50 values between 1and 8.3 mg mlÀ ). guillainii (ex Homalium pronyense), has been studied. Five new apotirucallane derivatives,dysorones A* –E*, Four alkaloids with amacrocyclic spermidinestructure

Fig. 24. Originalsulfurated tropane alkaloid found in Rhizophoraceae Fig. 26. Original hopane triterpene isolated from H. austrocaledonicus Fig. 27. Examples of original bioactive triterpenes isolated from Meliaceae were isolated fromthe leaves of Dysoxylum roseum Thechemistryofthree Tristaniopsis species (Trista- together with b-sitosterol. DysoroneE*(see Fig.27), the niopsis callobuxus, Tristaniopsis yateensis,and Tristaniopsis major compound, exhibited anti KB activity (IC50 glauca)isalso described in the literature.They contain 1 3.5 mgmlÀ )[87]. Other Dysoxylum species may contain ellagic acid and another original tannin called 3,4,5- further original bioactive triterpenes. trimethoxyphenyl(6-O-galloyl)-b-d-glucopyranoside [94]. Myrtaceae. This family is the most represented in New These plants demonstrated in vitro antiplasmodial activ- Caledonia. It contains 22 genera, including six endemics, ities.Ellagic acid and glycoside A3A were identified as and 257 species,only three being non-endemic: antimalarial active compounds(IC50 0.5 and 3.2 mm,resp.) quinquenervia, Sannantha virgata,and Syzygium mala- and exhibited very low cytotoxic activities on human skin ccense.Myrtaceae are often described in the literature for fibroblast cells and HepG2[94][95]. Recently,bioguided containing essential oils,terpenes,and flavonoids [88]. fractionationofleaf extract from Carpolepis laurifolia for Despite the importance of this group,only afew species antiviral activity against DENV has led to the isolation of have been investigatedyet. Forexample, we were unable to betulinic acid and five apigenin derivatives,includingan find any publication concerning the endemic Syzygium spp. unusual C-methylapigenin [96]. although Syzygium is the third most important genus in Other species may containvaluablechemicals,such as New Caledonia (71species). polyphenols with antioxidant or dying properties.Also, Volatiles from several endemic species have been fruit chemistryseems to be interestinginthis family since analyzed. Thus,the essential oils obtainedfrom the leaves severalspecies (e.g.,from Eugenia and Syzygium genera) of all seven endemic Melaleuca species were analyzed. produce aromatic and tasty fruits. They were shown to contain high amountsofmono- and . This family is representedinNew Caledonia sesquiterpene hydrocarbons [89].Essential oils from by 86 species,including 77 endemics,and is dividedinto 22 endemicspecies were significantly differentfrom the one genera.Rutaceae is widely known for its alkaloid-contain- obtainedfrom M. quinquenervia (niaouli)which is known ing genera. More than 60 alkaloids were isolated from to contain various sesquiterpene alcoholsand to exhibit Boronella, , Sarcomelicope, Myrtopsis, Geijera, antimicrobialactivity [90][91].Essential oils obtained Comptonella, Dutaillyea, Zanthoxylum,orFlindersia spe- from three Eugenia species have also recently been cies [18][97]. Someofthese compounds,such as acrony- analyzed for chemotaxonomical reasons[92]. Thus, Euge- cine derivatives,showedpotent antitumor activities.Some nia gacognei, Eugenia horizontalis,and Eugenia noumeen- examples representing the diversity of the original struc- sis were shown to contain acetophenone derivatives tures found in New Caledonian species are presented in together with mono-and sesquiterpenes [92].Finally,leaf Fig. 28. essential oil from Arillastrum gummiferum,the only Alkaloids from Rutaceae are furoquinoline, acrony- member of the endemic genus Arillastrum,has been dine,acronycine, acridone,orindole derivatives and there- investigated:itcontains limonene (80%),other monoter- fore should be associated with many bioactivities.How- penes,such as a-and b-pinene,and caryophyllene was the ever,only few biological evaluations of these plants have major sesquiterpene [93].Weshould notice that this tree is been published. Otherwise,coumarins were isolated from characteristic for some of the biotopeswecan observe on severalNew Caledonianspecies:ramosin,myrsellin*, and serpentinesoils,forming monospecific forests in some myrsellinol* (see Fig. 29)were isolated from leaves of cases.Ithas been extensively exploited in the pastfor Myrtopsis sellingii and Myrtopsis corymbosa [18][98]. carpentry,seeing its population highly reduced, and is now Other previously described coumarins are also represented threatened by mining activities (see www.oeil.nc). This tree in Myrtopsis spp., such as bergapten, phellopterin, seselin, should be integrated into reforestation plans and abetter and osthol, this class of compounds is showing cosmetic knowledge of its chemistry could give supplementary potential, such as for sun-protection [99].These plants also reasonsfor that. containunusual alkaloidssuch as myrtopsineand 8- Fig. 28. Examples for significative diversity of original alkaloidsisolated from Rutaceae

Fig. 29. Original and unusualcoumarins encountered in Rutaceae methoxyflindersine* (see Fig.28), triterpenes,and sterols ple in Fig.30)were isolated from leaves of Guioa crenulata (lupeol and sitosterol)[18]. [101]. Despite the fact that Rutaceae express ahigh econom- Otherwise,linear triterpenes called cupaniopsins A* – ical potential, these plants remain widely unexplored. Also, E* were isolated from barks of Cupaniopsis azantha, no investigation of the volatiles from any endemic species Cupaniopsis phalacrocarpa,and Cupaniopsistrigonocarpa has been done yet, despite the fact that oil bodies beneath and were evaluated for theiractivities against peroxisome their leaves are characteristic for Rutaceae.Moreover, proliferator-activated receptor-g (PPAR-g)[102]. The endemic Rutaceae are mostly representedonserpentine mostpotent compound,cupaniopsin A* (Ki 15 nm), is soils and should be further investigatedtofind new presented in Fig. 30.AsGuioa gracilis extracts are usedin economic justifications for their integration into revegetal- cosmetics and pharmaceutical preparations for treatment ization programs aftermining prospection and exploita- of skin aging [103], Guioacrenulata and Guioa villosa were tion. subjected to bioguided fractionationfor tyrosinase inhib- Sapindaceae. This family is represented in New Cale- itory activity.This study led to the isolation of seven donia by 71 species,including65endemics,and is divided farnesyl diglycosides called crenulatosidesA*–G* (see into 14 genera.Triterpenoidsaponins and acylated prosa- two examples in Fig. 30), flavonoids,one trimeric proan- pogenins were isolated from stem barkofHarpullia thocyanidin,two triterpenes,and acerebroside called austrocaledonica [17][100]. Four original acylated farnesyl soyacerebroside I(see Fig.30)which appearedtobea diglycosides called crenulatosides A* –D*(see one exam- potent tyrosinase inhibitor [104]. Fig. 30. Examples of original and bioactive sesquiterpene and triterpene derivativesisolated from Sapindaceae

Simaroubaceae. are representedinNew sa [108 –110], soulameanone*, 1,12-diacetylsoulameanone, Caledonia by eleven endemic Soulamea species. According and D2-picrasin B* from Soulamea muelleri [111].Finally, to the literatureavailableonthis family [105][106], the the study on Soulamea fraxinifolia led to the isolationofa investigation of endemic Soulamea speciesled to the coumarin (scopolerol), two alkaloids (1-(2-hydroxyethyl)- isolationofnumerous quassinoids:picrasin Band 6- b-carboline*, and pavettine*),and quassinoids (includ- hydroxypicrasin B* from Soulamea pancheri [107], isobru- ing D2-picrasin B* and isobrucein A*) [112]. Original cein A* and soulameolide(also foundinQuassia indica) compounds isolated from this family are presented in and antileukemic soularubinone* from Soulamea tomento- Fig. 31.

Fig. 31. Original compoundsisolated from Simaroubaceae Fig. 32. Original flavone derivativesisolated from L. salicifolia Strasburgeriaceae. This family is only represented by This review compiles publisheddata concerning the the endemic species Strasburgeria robusta.Three known chemistryofNew Caledonian basal angiosperms (14 saponins were isolated from the stem bark of this plant: 1- families,176 species including 160 endemics), monocots O-(24-hydroxytormentoyl)glucopyranoside and nigaichi- (29 families,572 species including 276 endemics), and gosides F1 and F2[113]. No biological test was associated eudicot rosids (56families,1287 species including 1093 with this study,but related saponins previously showed endemics).Wefocused on endemic species and present an pharmacological activities and more generally,saponins are update of original compounds that can be considered as associated with various traditional and industrial applica- specific to New Caledonian flora. We also highlighted tions,such as for fish poisoning and production of steroid economic perspectivesfor these natural compoundsand hormones for the pharmaceutical industry [114]. Also,an endemic plants. Thus,this reviewcompiles data provided improved knowledge of the chemistry of S. robusta could by 60 articles dealing specifically with chemical investiga- allow abetter understanding of its isolated and ancestral tions of endemic basalangiosperms and eudicot rosids and positioninthe phylogenic tree (see Fig.1). includes more than 60 previous articles also dedicated to Thymelaeaceae. This family is represented in New these plantscited in aprevious review by SØvenet and Caledonia by 19 species,all but one beingendemic. New Pusset. Caledonian Thymelaeaceaeare divided into four genera, According to the bibliographywesummarized here,we including the two endemic Deltaria and Solmsia.Only one identified225 original compoundsthat are specific to New endemic species was studied in New Caledonia: Lethedon Caledonianendemic species.Until now,phytochemical salicifolia (ex Lethedon tannensis). research mainlyfocused on alkaloids and terpenoids, Investigation of aleaf extractfrom this plant led to leading to the discovery of 83 and 47 original structures, isolation of several 5-hydroxy-7-methoxyflavones and respectively3). This is clearly linked to the research of glycoside derivatives,includingoriginal lethedosides A* – bioactivecompounds for pharmaceutical applications.This C*, lethediosides A* and B*, and lethedocin* (see struc- reviewhighlighted the economic potential of several plants, tures in Fig.32). These flavones showed cytotoxic activities such as from Annonaceae, Clusiaceae,and Rutaceae againsthuman nasopharynx carcinoma KB cells families.Inmost cases,alot of work remains to be done [115][116]. This family remains vastly unexplored, espe- before industrial application. However,for some plants cially regarding the endemic genera Deltaria and Solmsia that contain heavy metal binders,the chemical synthesis of that are dedicated to serpentinesoil and thus are especially thesecompounds is studied, and they should be soon threatened by mining activities and degradations. exploitedfor industrial utilization. This project is closely associated with revegetalizationofserpentine soils and is a Conclusions. –Asshown in several recent review perfect example of the economic potential of the New articles,natural products offer new perspectives for indus- Caledonianplant diversity.Itillustrates the necessity to trial innovations,such as for pharmaceutical or cosmetic protect the New Caledonian flora and to pursue its applications.This renew of interestinnatural compounds is chemical investigation. both relatedtoecological preoccupations and to the great Severalfamiliesthat provedtocontain interesting and/ extent of tools available for phytochemical studies [117]. or original compounds are still largely unexplored,for As an example,couplingpossibilities offered by new example Euphorbiaceae,Myrtaceae,and Celastraceae. chromatographic instruments,such as 2D-LCassociated Manygroups have remained completely untouched despite with HR-MS or NMR withhigh throughput screenings and the fact that several of them seem to be particularly moderninformatics software,allowed the beginningof attractive for phytochemical investigations.Though A. efficient complex mixture studies (metabolomics,syner- trichopoda is considered as the mostbasal floweringplant gies, etc.). We hope that this new economic interest in naturalcompounds will encourage the protection of 3)Compounds are considered as originals when encountered only in particular original biotopes called hot spots and of the arestricted numberofendemic species stemming from aunique New Caledonianflora. genus. in the world, no chemical investigation of this plant has [23] A. Bermejo,B.Figad›re,M.-C.Zafra-Polo,I.Barrachina,E. been performed yet. However, such an investigationcould Estornell, D. Cortes, Nat. Prod. Rep. 2005, 22,269. lead to interesting resultsfor chemotaxonomy and plant [24] Phytochemistry of Plants Used in Traditional Medicine, Eds.K. Hostettmann, A. Marston, M. Maillard,M.Hamburger, Claren- evolution. Also,none of the endemic monocots has been don Press,Oxford, 1995. investigatedyet. Finally,Chloranthaceae (three endemic [25] R. S. Rattan, Crop Prot. 2010, 29,913. species),Piperaceae (15 species including eight endemics), [26] N. Aminimoghadamfarouj, A. Nematollahi,C.Wiart, J. Asian Nat. Elaeocarpaceae (47 species including 44 endemics), Pic- Prod. Res. 2011, 13,465. rodendraceae (18 species including17endemics), and [27] A. Jossang,M.Lebœuf,P.Cabalion,A.CavØ, PlantaMed. 1983, Phyllanthaceae(120 species including113 endemics)which 49,20. [28] R. Hocquemiller, C. Debitus,F.Roblot,A.CavØ, H. Jacquemin, J. have not been investigated either, are,according to our Nat. Prod. 1984, 47,353. opinion, prime targets for the searchoforiginaland [29] M. Toussirot, W. Nowik, E. Hnawia, N. Lebouvier,A.-E. Hay,A. bioactive compounds. de la Sayette,M.-G.Dijoux-Franca, D. Cardon, M. Nour, Dyes Pigm. 2014, 102,278. Theauthors are thankfultoall researchers working for increasing [30] G. Marti, V. Eparvier,B.Morleo,J.LeVen, C. Apel, B. Bodo,S. the knowledge of New Caledonian plants and promoting their Amand, V. Dumontet, O. Lozach, L. 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