Triterpenoids

Joseph D. Connolly and Robert A. Hill Department of Chemistry, Glasgow University, Glasgow, UK G12 8QQ Received (in Cambridge, UK) 21st August 2003 First published as an Advance Article on the web 23rd October 2003
Covering: 2001. Previous review: Nat. Prod. Rep., 2002, 19, 494 This review covers the isolation and structure determination of triterpenoids including squalene derivatives, lanostanes, cycloartanes, dammaranes, euphanes, tirucallanes, tetranortriterpenoids, quassinoids, lupanes, oleananes, friedelanes, ursanes, hopanes, fernanes, sipholanes, isomalabaricanes, serratanes and saponins. The literature from January to December 2001 is reviewed and 242 references are cited. 1 2 3 4 4.1 4.2 5 6 7 8 9 10 1 Introduction The squalene group The lanostane group The dammarane group Tetranortriterpenoids Quassinoids The lupane group The oleanane group The ursane group The hopane group Miscellaneous compounds References

Introduction

The biological activities of triterpenoids continue to be of interest. Reviews have appeared on the aphrodisiac properties of the triterpenoids from Panax ginseng,1 the biological activities of triterpenoids from liquorice root 2 and antimycobacterial plant terpenoids.3 The anti-tumourogenic properties of ursolic acid 4 and the possible use of celastrol for the treatment of Alzheimers disease 5 further emphasise the biological importance of triterpenoids. The use of terpenoids, including triterpenoids, as chemosystematic markers in conifers has been discussed.6 2 The squalene group

Armatols AF 16 are brominated squalene derivatives from the Indian Ocean alga Chondria armata.7 The complete stereochemistry of the epoxysqualene tritetrahydrofurandiol 7 from Spathelia glabrescens 8 has been conrmed by synthesis.9 Concentricol 8 is a squalene hexol from Daldinea concentrica.10 The bis-epoxide auriculol 9 has been isolated from Dolabella auricu-

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DOI: 10.1039/b204068a

laria.11 Four new squalene ethers have been found in Laurencia viridis.12 These include martiriol 10, pseudodehydrothyrsiferol 11, dioxepandehydrothyrsiferol 12 and 16-epihydroxydehydrothyrsiferol 13. Four irregular triterpenoids 1417 have been isolated from the marine diatom Rhizosolenia setigera.13 Testudinariols A 18 and B 19 from Pleurobrancus testudinarius have been synthesised.14 The absolute conguration of longilene peroxide 20, isolated from the wood of Eurycoma longifolia, has been established by synthesis.15 Molecular modelling studies have revealed that the original structure proposed for glabrescol 21 is not the most thermodynamically stable and therefore synthetic evidence was very important in the structure elucidation.16

The lanostane group

The squalene cyclase from the bacterium Zymomonas mobilis demonstrates its lack of specicity by producing a range of polycyclic metabolites including - and -polypodatetraenes 22 and 23, dammara-20,24-diene 24, 17-isodammara-12,24-diene 25, eupha-7,24-diene 26, hop-17(21)-ene 27, neohop-13(18)-ene 28, 17-isodammara-20,24-diene 29, neohop-12-ene 30, fern-8ene 31, diploptene 32, and hop-21-ene 33.17

Alisol F 24-acetate 34 is a new protostane from Alisma orientalis.18 New metabolites of Ganoderma lucidum include lucidenic acid N 35 (lucidenic acid LM1) and methyl lucidenate F 36.19 Three new pentanorlanostane derivatives, cladosporides B 37, C 38 and D 39, have been isolated from a Cladosporium sp.20 Cladosporides A and B show antifungal activity against Aspergillus fumigatus. A new 21,24-cyclolanostane derivative 40 has been reported from the wood rotting fungus Inonotus obliquus.21 Fuscoporianol A, which is the 25-O-methyl ether of 40, occurs in Fuscoporia obliqua together with B 41 and C 42.22 The structure of fuscoporianol A was conrmed by X-ray analysis. The structure of ananosic acid A 43, an unusual rearranged lanostane from the stem bark of Kadsura ananosa, has been conrmed by X-ray analysis.23 Other new lanostanes include the trienes 44 and 45 from Guarea rhophalocarpa,24 sublateriols A 46, B 47 and C 48 from the edible mushroom Naematoloma sublateritium 25 and 3,24-dihydroxy-24-methyllanost-8-en-30-oic acid 49, together with the lanostane saponin formoside B, from the Caribbean sponge Erylus formosus.26 Feroxosides A 50 and B 51 are nor-lanostane saponins from Ectyoplasia ferox.27 Erylosides GJ, lanostane saponins from the sponge Erylus nobilis, have new genins 52 and 53.28 Colossolactones AG 5460 form an interesting series of lanostanes and modied cycloartanes from the mushroom Ganoderma colossum.29 It should be noted that colossolactone A 54 is not actually a lactone. Schiprolactone A 61, from Schisandra propinqua, has a novel side chain.30

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Two unusual cleaved cycloartanes, pseudolarolides E 62 and F 63, have been reported from Pseudolarix kaempferi.31 Their structures were established by X-ray crystallographic analysis. Five 29-nor-3,4-seco-cycloartanes 6468 have been isolated from Antirhea acutata.32 The aerial roots of Ficus microcarpa contain the 27-nor-derivative 69 and the 25,26,27-trinorderivative 70.33 Compound 71 and cycloabyssinone 72 are nor-cycloartanes from Artemisia caruifolia 34 and Harrisonia abyssinica,35 respectively. Other new cycloartanes include tillandsinone 73 and cyclolaudenyl formate 74 from Tillandsia fasciculata,36 the acetate 75 from Dysoxylum malabaricum,37 and compounds 76 and 77, together with many triterpenoid

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The constituents of Cimifuga species have been reviewed.40 Four new saponins, bugbanosides C 79, D 80, E 81 and F 82 have been isolated from Cimifuga simplex.41 A new cimigenol glycoside 83 and two trinor-derivatives 84 and 85, with new genins, have been reported from Cimifuga dahurica.38,42 Actaeaepoxide 3---xylopyranoside 86 is a new glycoside from Actaea racemosa (Cimifuga racemosa).43 Other new compounds from Cimifuga racemosa include 8797 44 and 25-O-methylcimigenol 3-O---arabinopyranoside (cimiracemoside B).45 2 -O-acetylactein 92 and 2 -O-acetyl-27-deoxyactein 93 are constituents of Cimifuga foetida 46 while 22R-hydroxycimifugol 94 and the shengmanol derivative 95 are found in Cimifuga acerina.47

esters, from the owers of Chrysanthemum morifolium.38 Thalictoside F is a new saponin from Thalictrum thunbergii with the new genin 78, the 21,24-diepimer of thalictoside E.39 The full details of the structure elucidation of thalictosides D and E are included in this paper. Nat. Prod. Rep., 2003, 20, 640659 643

Askendosides G and A and cycloglobiceposide B are known cycloartane saponins from Tragacantha stipulosa.48 Astragalus prusianus contains two new saponins prusianosides A 96 and B 97.49 New cycloartane saponins have also been reported from Astragalus trojanus (trojanosides IK) 50 and Astragalus caprinus.51

Liouvillosides A and B are sulfated holostane glycosides from Staurocamis liouvillei.52 Patagonicoside A, a holostane glycoside with a new aglycone 98, has been isolated from Psolus patagonicus.53 The aglycone 99 of frondoside F, a minor saponin constituent of the sea cucumber Cucumaria frondosa, contains an unusual 18 22 lactone.54

Neocucurbitacins A 100 and B 101, from the Brazilian folk medicine Buchinha (Lua operculata), have an inhibitory eect on some gene expression in a human osteoblast-like cell line.55 Momordica charantia is a rich source of triterpenoid saponins. The new cucurbitacin derivatives, goyaglycosides AH 102109, were accompanied by known cucurbitane 644 Nat. Prod. Rep., 2003, 20, 640659

saponins and oleanane saponins (goyasaponins IIII).56 The aldehyde 110 has been obtained from an extract of the whole plant of Momordica charantia.57 Two seco-cucurbitane derivatives 111 and 112 have been isolated from Russula lepida.58

The dammarane group

The structures of 15-acetoxycleomblynol A 113, from Cleome amblyocarpa,59 and cabraleadiol 3-acetate 114, from Aglaia lawii,60 have been established by X-ray analysis. The 20S,24S stereochemistry of cabraleadiol is thus established. Other new dammaranes include 115 and 116 from the fruits of Forsythia suspensa 61 and semialactone 117, isofouquierone peroxide 118 and fouquierone 119 from Rhus javanica.62

New dammarane saponins continue to appear. The hexanorderivative notoginsenoside R10 120 has been found in the roots of Panax notoginseng.63 Ginsenosides Rh5 121, Rh6 122, Rh7 123, Rh8 124 and Rh9 125, from the leaves of Panax ginseng, all apart from Rh7 123 have new genins.64 Polysciasoside A 126, from Polyscias fulva, is a saponin of 3,16,20S-trihydroxydammar-24-en-12-one.65 Two new glycosides, notoginsenosides T1 127 and T2 128, have been isolated following mild acidic hydrolysis of the crude root saponins of Panax notoginseng.66 A method for regioselective enzymatic galactosylation and glucosylation of protopanaxatriol ginsenosides has been published.67 Papers on new dammarane saponins include bacopasides I and II from Bacopa monniera,68 quinquenosides L1, L2 and L9 from the leaves and stems of Panax quinquefolium,69 notoginsenosides L, M and N from Panax notoginseng,70 ginsenosides I and II from the ower buds of Panax ginseng 71 and ginsenoside Rh5 and vina-ginsenoside R25 from Panax vietnamensis.72 Nat. Prod. Rep., 2003, 20, 640659 645

another, 138, was found in Dysoxylum malabaricum.37 Other compounds in this series include the apotirucallane 139 from Azadirachta indica,75 the 14,18-cycloapotirucallanes 140 and 141 from Guarea jamaicensis 76 and the nor-derivatives malabanones A 142 and B 143 from Ailanthus malabarica.77

A new homocyclotirucallane, sinetirucallol 129, has been isolated from Spiranthes sinensis.73 Its structure was established by X-ray analysis. Eight new tirucallanes, dyvariabilins AH 130137, have been reported from Dysoxylum variabile 74 while

4.1

Tetranortriterpenoids

Many new limonoids have appeared this year. The three hirtin derivatives 144146, from Trichilia pallida, show antifeedant activity.78 Meliacinolactol 147, limocin C 148 and limocin D 149 are further constituents of Azadirachta indica.79 Further rearranged limonoids from Harrisonia perforata include haperforins C2 150, F 151 and G 152.80 Their structures were 646 Nat. Prod. Rep., 2003, 20, 640659

from Evodia rutaecarpa,85 21-O-methyllimonexic acid 160 and 8,14-epoxyfraxinellone 161 from Raulinoa achinata 86 and 1-Omethylichangensin 162 and sudachinoids A 163, B 164 and C 165 from Citrus sudachi.87 Polygonumins A 166 and B 167 are the E- and Z-feruloyl esters of desacetylnomilin from Polygonum orientale.88 1,2-Dihydroamoorinin 168 is a new limonoid from Aphanamixis polystacha.89 Three new ring C cleaved derivatives, melianol 169, desfuranodesacetylnimbin17-one 170 and meliatetraone 171, have been reported from the leaves of Azadirachta indica.90

determined by X-ray analysis, as were those of 7-isovalerylcycloseverinolide 153 and 7-isovalerylcycloepiatalantin 154 from the root bark of Severinia buxifolia.81 Pterorhachis zenkeri contains 9-amoorstatin 155 and 3-deacetylamoorstatin 156.82 The ring D unsaturated -lactone, deoxyobacunone 157, from the root bark of Harrisonia abyssinica, shows stimulatory activity against Striga hermonthica seeds.83 Other new limonoids include cedrellin 158 from Cedrela sinensis,84 shihulimonin A 159 (previously isolated in 1965 and named limonexic acid) Nat. Prod. Rep., 2003, 20, 640659 647

4.2

Quassinoids

New quassinoids include cedronolactone 178 from Simaba cedron,94 12-epi-11-dehydroklaineanone 179 from Eurycoma longifolia,95 iandonoside A 180, B 181 and iandonone 182 from Eurycoma harmandiana 96 and 16-O-methylneoquassin 183 and 16-O-ethylneoquassin 184 from the wood of Picrasma crenata.97

The full details for the structures of khayanolides A and B, from Khaya senegalensis, have appeared and a new compound, khayanolide C 172, has also been obtained.91 In a separate paper, three further derivatives, 1-O-acetylkhayanolide 173, khayanone 174, and 2-hydroxyseneganolide 175, are described from Khaya senegalensis.92 The structures of two limonoids, febrifugin 176 and cipadesin 177, from Cipadessa baccifera, have been conrmed by X-ray analysis.93

The lupane group

Sachunoside is a seco-abeo-lupane saponin from Acanthopanaz divaricatus var. sachunensis.98 The aglycone is sachunogenin 185. The acid 186 and hydroperoxide 187 occur in Ficus microcarpa.99 Other new lupanes include 6-hydroxybetulinic acid 188 from Eugenia moraviana,100 lup-20(29)-ene-1,2,3-triol 189 from Cephalomappa sinensis,101 21-hydroxylupa-1,12-dien3-one 190 from the roots of Hemidesmus indicus,102 and 2,6dihydroxybetulinic acid 191 (isolated in 1999 as divergioic acid) and 6-hydroxyhovenic acid 192, which is the aglycone of quadranoside II, from Combretum quadrangulare.103 The 3,7dibenzoate 193 and the 7-benzoate 194 of 3,7-dihydroxylup20(29)-en-28-oic acid have been isolated from the stem bark of Picramnia teapensis.104 Ulmicins AE 195199 are lupane esters from Ulmus davidiana var. japonica.105 Other esters include 200 from Mimusops elengi,106 lawsonic acid 201 from

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lupane saponins, isolated from Pulsatilla chinensis, include one new genin 3,20,23-trihydroxylupan-28-oic acid 204.110 Coccinioside K is a betulinic acid saponin from Coccinia indica 111 and a lupane saponin has been isolated from Arenaria licaulis.112

The oleanane group

Trypterygium wilfordii is a rich source of oleanane, friedelane and ursane triterpenoids.113 In addition to the nor-oleanane 205 and the seco-oleanane 206, it produces the lactone 207, the carboxylic acids 208211, the friedelanes 212 and 213 and the nor-friedelane 214. Interestingly, compounds 212 and 213 have

Lawsonia alba,107 and 202, 203 and a range of 3-O-acyl esters of lupeol from Parahancornia amapa. 108 The twig bark of Pyrus serotina contains a further ve fatty esters of lupeol.109 Four Nat. Prod. Rep., 2003, 20, 640659 649

Dioxoolean-18-en-28-oic acid 226 is a constituent of Acacia aulacocarpa.122 The 3,4-seco-derivative 227 has been isolated from Phoradendron reichenbachianum.123 The 3,22-diol, -sophoradiol 228, has been reported from the stem of Erythrina sigmoidea.124 The hydroperoxide 229 has been found in the aerial roots of Ficus microcarpa.99

an additional two carbon fragment attached to C-6. The lactones melliferone 215, 216 and patrinolide A 217 have been reported from Brazilian propolis (Myrceugenia euosma),114 Nigella sativa 115 and Patrinia scabiosaefolia,116 respectively. The range of polyhydroxyoleanenoic acids includes the triol 218 from the fruit of Rosa davidii,117 the tetrol buergericic acid 219 from Rubus buergeri,118 6-hydroxyarjunic acid 220 from Combretum quadrangulare,103 the triol 221 from Eriobotrya deexa 119 and cucubalugenin A 222 from Cucubalus baccifer.120 Hemidesmusyl acetate 223, from Hemidesmus indicus, apparently lacks a C-3 oxygen substituent 102 as does the 27-noraldehyde 224 from the roots of Lavandula stoechas ssp. stoechas.121 It is accompanied by the aldehyde 225. 3,21-

Papers have appeared on the triterpenoids of the stem bark of Albizzia versicolor and A. schimperana,125 pyrotechnoic acid 230, an ether of oleanolic acid from Leptadenia pyrotechnica,126 and tetra-, penta- and hexadecanoyl esters of oleanolic acid.127 Four new esters 231234 have been reported from Lippia turbinata 128 and one 235 from Eugenia sandwicensis.129 The

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Table 1 New oleanane saponins Compound(s) Albiziatrioside A Anhuienosides AF Araliasaponins VIX Arjunetoside Basellasaponins AD Beesioside Q Bidentatoside I Bidentatoside II Calendsaponins AD Centellasaponin D Chikusetsusaponin V methyl ester Clematibetosides AC Colchisides A and B Conyzasaponins AG Congmunosides V, VII, XV, XVI Crataegioside Eclalbasaponins XI and XII Eclabatin Escins Ivg, Ivh and Vib Eupteleasaponin VIXII Glycoside D2 Glycosides LC2 and LI2 Glycosides StC2, StD1, StD2 Glycosides StE2, StF2, StJ2, StK2 Glycosides StH2, StI2 Junceosides AC Latifolosides IQ Maetenosides A and B Pisumsaponins I and II Prostratosides D and E Prostratosides FH Protoprimuloside B Saikosaponin q-1 Saikosaponins V-1 and V-2 Securiosides A and B Sinofoside A Subcapitatosides B and C Tanguticosides A and B Vitaboliside A 2 -methylglucuronate Zygoeichwaloside I Source Albizia subdimidiata Anemone anhuiensis Aralia elata Terminalia arjuna Basella rubra Beesia calthaefolia Achyranthes bidentata Achyranthes bidentata Calendula ocinalis Centella asiatica Achyranthes bidentata Clematis tibetana Hedera colchica Conyza blinii Aralia elata Rubus crataegifolius Eclipta prostrata Eclipta alba Aesculus chinensis Euptelea polyandra Fatsia japonica Scheeropsis angkae Tetrapanax papyriferum Tetrapanax papyriferum Tetrapanax papyriferum Arenaria juncea Ilex latifolia Maesa tenera Pisum sativum Polycarpon prostratum Polycarpon prostratum Primula elatior Bupleurum chinense Bupleurum chinense Securidaca inappendiculata Sinofranchetia chinesis Aralia subcapitata Clematis tangutica Albizia gummifera Zygophyllum eichwaldii Ref. 142 143 144 145 146 147 148 149 150 151 149 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180

complete proton and carbon NMR assignments of several oleanane and ursane triterpenoids from Mentha villosa have been published. 130 Crystal structures have been published for wilforlide A 130 from Trypterygium wilfordii 131 and 3methoxyolean-18-ene (meliacin) from the marine fungus Chaetomium olivaceum. 132 The 24,30-dinor-oleanane derivative 236 has been found in Paeonia delavayi 133 while the 24,28-dinor-compound remangilone D 237 occurs in Physena madagascariensis.134 A 27-nor-

oleanane 238 has been reported from the stem bark of Vitis vinifera.135 Camelliosides AD are oleanane saponins, from Camellia japonic, with known genins.136 An X-ray crystal structure analysis of camellenodiol, the genin of camelliosides A and B, revealed that it is 239 with a 28- and not an 18-hydroxyl group. The structure of the corresponding ketone, camellendionol, should be revised to 240. Three saponins, one of which has the new genin gymnemagenol 241, have been isolated from Gymnema sylvestre.137 A new saponin anemoside B together with a new oleanane anemonolide 242 have been reported from Anemone rivularis.138 Fargosides AE are new saponins from Holboellia fargesii.139 Fargoside B has a new genin, the 29-nor-oleanane derivative 243. The new saponin 244, from Terminalia arjunis, also has a new genin.140 Centellasaponin A, from Centella asiatica, has the new genin 245.141 New oleanane saponins that have been assigned trivial names are listed in Table 1.

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acetal 3,24-epoxy-24-ethoxy-2-hydroxyfriedelan-29-oic acid, whose structure was conrmed by X-ray analysis.199 A dinorfriedelane, 6-hydroxytriptocalline A 253, has also been isolated from Tripterygium wilfordii.200 Other new friedelanes include calotropfriedelenyl acetate 254 from Calotropis procera,201 3-methoxyfriedel-2-en-1-one 255 from Salacia petenensis 202 and three 27,16-lactones 256258 from Mallotus repandas.203 The structure of lactone 257 was conrmed by X-ray analysis. The bis-friedelane derivative scutionin B 259 has been reported from Maytenus blepharodes and M. magellanica together with the corresponding 6 ,7 -dihydro- and 6-methoxy-6 ,7 -dihydro-derivatives.204

New oleanane saponins, that have not been assigned trivial names, have been isolated from: Acanthophyllum squarrosum,181 Astragalus trigonus,182 Bellis perennis,183 Chenopodium quinoa,184 Elattostachys apetala,185 Fagonia cretica,186 Fatsia japonica,187 Glycyrrhiza sp.,188 Isertia pittieri,189 Ixeris sonchifolia,190a Koelreueria paniculata,190b Phytolacca americana,191 Sanguisorba ocinalis,192 Sapindus emarginatus,193 Scheera arboricola 194 and Terminalia alata.195 The structure of the multiorane derivative 246 from Momordica cochinchinensis has been conrmed by X-ray analysis.196 Sandorinic acids A 247, B 248 and C 249 are three multioranes from Sandoricum indicum.197

The ursane group

Two seco-friedelanes 250 and 251 have been isolated from the leaves of Austroplenckia populnea.198 The nor-seco-derivative 252 is accompanied in Tripterygium wilfordii by the known

Two ursane hydroperoxides 260 and 261 and a cyclic peroxide 262 have been isolated from Ficus microcarpa.99 The structure of 262 was conrmed by Xray analysis. The aerial roots of Ficus macrocarpa contain two 13,27-cycloursanes 263 and 264.33 The structure of the former was conrmed by X-ray analysis. Swinhoeic acid 265 is an unusual 18,19-seco-ursane

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from Rubus swinhoei.205 The 16,17-seco-derivatives secohemidesursenyl acetate 266 and seco-hemideursenol 267, from Hemidesmus indicus,102 and the 14,15-seco-compound 268, from Pluchea lanceolata,206 have also been reported. Six antiandrogenic ursanes: cordiaketals A 269 and B 270, cordianone 271 and cordianals A 272, B 273 and C 274, have been isolated from the leaves of the Brazilian plant Cordia multispicata.207 The highly oxygenated 2,3,19,25-tetrahydroxyursene-23,28dioic acid 275 is a constituent of Rhaponticum uniorum.208

Two ursane methyl ethers 276 and 277 have been found in Salvia roborowskii.209 Lawsonia alba contains the feruloyl ester 278.107 Other ursanes include: the diene 279 from Rubus chroosepalas,210 the lactone 280 from the fruit of Rosa davidii,117 calotropursenyl acetate 281 from Calotropis procera,201 actinidic acid 282, a phytoalexin from unripe Kiwi fruit,211 two 30-

carboxylic acids 283 and 284 from Trypterygium wilfordii,113 the keto-triol-acid 285 from Eriobotrya deexa,119 and urs-12-ene3,6,19,23-tetrol 286 from Mimusops elengi.106 30-Nor-urs12-ene-3,19-diol 287 is a constituent of Debregeasia salicifolia 212 while 19,24-dihydroxy-3-oxo-12-ursen-28-oic acid 288 occurs in Rhododendron simsii.213 The feruloyl ester 289 is found in Eriobotrya japonica.214 Five new ursane saponins have been reported from Tupidanthus calyptratus, with two new genins 290 and 291.215 Kudinosides IP are new ursane saponins from the leaves of Ilex kudincha.216 Kudinolic acid 292 is the aglycone of kudinosides IK. Zygophyloside N is another ursane saponin with a new genin 293, from Zygophyllum gaetulum.217 Urs-12Nat. Prod. Rep., 2003, 20, 640659 653

new taraxastanes 301, 302 and 303 have been reported from Saussurea petrovii.224 The diol 302 has also been found in Picris evae.225 22-Methoxyfaradiol 304 and its 3-palmitate are constituents of the owers of Chrysanthemum morifolium.38

ene-3,21,28-triol 294 is the new genin of latifoloside I from Ilex latifolia where it occurs with latifoloside J which has a known genin.218 The 20S-isomer of the 28-O --glucopyranosyl ester of rotundioic acid 295 has been claimed as a constituent of the leaves of Ilex argentina.219 Two new saponins 296 and 297, with known genins, have been isolated from Centipeda minima.220 Other ursane saponins with known genins include centellasaponins B and C from Centella asiatica,151 latifolosides K and L from Ilex latifolia bark 221 and constituents of Clematoclethra scandens 222 and Sanguisorba ocinalis.192 The resin of Protium heptaphyllum contains the new ursane 298 together with two taraxastanes 299 and 300.223 Three 654 Nat. Prod. Rep., 2003, 20, 640659

The hopane group

Three isomeric series of hopanoids, 17,21, 17,21 and 17,21, have been detected in several Frankia species and other soil bacteria. Their presence raises fundamental questions concerning the biosynthesis of the bacteriohopanes.226 32,35Anhydrobacteriohopanetetrol 305 has been identied in Plakortis simplex.227 Other new hopanes include 306 228 and the nor-epoxide 307 229 from Adiantum lunulatum and the diol acetate 308 from Aschersonia tubulata.230 The neohopane caeate 309 has been reported from Filicum decipiens.231 Spergulins A and B are hopane saponins with known genins.232

carbon NMR assignments of fern-9(11)-en-28-oic acid have been published.234 9 Miscellaneous compounds

Hoogianal 313 is a new constituent of Iris hoogiana.235 A range of sipholane derivatives has been identied in Siphonochalina siphonella including sipholenols F 314, G 315 and H 316, sipholenone D 317, sipholenosides A 318 and B 319, neviotine B 320, siphonellinol B 321 and dahabinone A 322.236 New isomalabaricane derivatives include 323325 from a Jaspis sponge,237 stelliferin riboside 326 from Geodia globostellifera 238 and the 27nor-derivatives geoditins A 327 and B 328 from Geodia japonica.239

8-Hydroxyfernan-25,7-olide 310, 3-hydroxy-4-methoxylicane 311 and 19-hydroxyferna-7,9(11)-diene 312 have been isolated from Adiantum caudatum.233 The complete proton and

Chirat-16-ene-3,24-diol 329 has been identied in Swertia chirata.240 The serratane epoxides 330, 331 and 332 have been isolated from Picea jezoensis var., jezoensis.241 The structures of 330 and 331 were conrmed by X-ray analysis. Adiantutirucallene B 333 and adiantulanostene B 334 are strange triterpenoids from Adiantum venustrum.242 Nat. Prod. Rep., 2003, 20, 640659 655

10

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