Isoflavonoid phytoalexins of the genus Medicago

Detached leaves of 25 annual and perennial Medicago species have been inoculated with the fungus, Helminthosporium carbonum, and examined for subsequent production of isoflavonoid phytoalexins. Hydroxylated pterocarpan (medicarpin) and isoflavan (vestitol, sativan and isosativan) phytoalexins were obtained from most of the species investigated. Although large quantities of two flavonoid derivatives, isoliquiritigenin and liquiritigenin, were isolated from leaves of M. lupulina, this species was apparently unable to produce isoflavonoid compounds. Traces of 7-hydroxy-2′,4′-dimethoxyisoflavanone (a substance not previously recorded in the tribe Trifolieae) were obtained (together with medicarpin, vestitol and sativan) from M. sativa cv Du Puits. Some taxonomic aspects of phytoalexin induction are discussed with reference to the generic location of certain controversial Medicago species including M. (Trigonella) radiata.     

Phytoalexin induction and its chemosystematic significance in the genus Trigonella

Using the drop-diffusate technique, a number of isoflavonoid phytoalexins have been obtained from the excised, fungus-inoculated leaflets of 41 species belonging to the legume genus Trigonella. Leaf diffusates variously contained pterocarpan (medicarpin and maackiain) and isoflavan (vestitol and sativan) derivatives previously associated with genera closely allied to Trigonella. In diffusates from T. calliceras, medicarpin was accompanied by a phytoalexin (designated TC-1) provisionally identified as a new hydroxylated pterocarpan. Most of the Trigonella species were also examined for their ability to release coumarin upon tissue maceration. The combined phytoalexin/coumarin data suggest that three major intrageneric chemical divisions occur in Trigonella; two of these apparently link the genus to Medicado/Factorovskya and Melilotus respectively, whilst the third provides some evidence for a connection with Trifolium. The taxonomic aspects of these findings are discussed in the light of earlier morphological studies which provided evidence for a distinct floral dichotomy amongst Trigonella species.     

Isoflavonoid phytoalexins from fungus-inoculated leaves of Apios tuberosa

A new phytoalexin (apiocarpin) isolated from the fungus-inoculated leaflets of Apios tuberosa has been identified by chemical and spectroscopic pro     

Two novel stilbene phytoalexins from Arachis hypogaea

Three phytoalexins were isolated from groundnut seeds which had been sliced and incubated for 48 hr at 252. Two were novel isoprenylated stilbene der     

New pterocarpan phytoalexins from Lathyrus nissolia

In addition to 3-hydroxy-9-methoxypterocarpan (medicarpin), the fungus-inoculated phyllodes of Lathyrus nissolia produce two previously unreported isoflavonoid phytoalexins. These compounds have been identified as 3,9-dihydroxy-10- methoxypterocarpan (nissolin) and 3-hydroxy-9,10-dimethoxypterocarpan (methyl-nissolin).     

New stilbene phytoalexins from American cultivars of Arachis hypogaea

Two phytoalexins from American varieties of Arachis have been characterized as the cis- and trans-isomers of 3,5,4′-trihydroxy-4-isopentenylstilbene.     

Phytoalexin production by Ononis species

Following exposure to short wavelength (254 nm) ultra-violet light, the detached leaflets of Passaea (Ononis) ornithopodioides and 31 species and subspecies of Ononis have been found to accumulate substantial quantities of the isoflavonoid (pterocarpan) phytoalexin, medicarpin. Apart from P. (Ononis) ornithopodioides, O. cristata, O. fruticosa, O. pubescens and O. rotundifolia, leaf tissues of all the species investigated similarly contained small amounts of the related fungitoxic pterocarpan, maackiain. Isoflavan phytoalexins common in genera such as Medicago and Trifolium (tribe Trifolieae) were absent from both Ononis and Passaea. The phytoalexin data suggest that Passaea should probably be combined with Ononis and, in conjunction with information on constitutive isoflavonoids, that Ononis itself should be assigned to the Trifolieae rather than to the distinct tribe Ononideae. Chemical evidence for and against an especially close taxonomic association between Ononis and Cicer (tribe Cicereae) is also briefly discussed.     

A new isoflavan phytoalexin from leaflets of Lotus hispidus

A new isoflavonoid phytoalexin isolated from the fungus-inoculated leaflets of Lotus hispidus (hairy birdsfoot trefoil) has been identified as 5,4′-dimethoxy-7,2′-dihydroxyisoflavan (5-methoxyvestitol). Three known isoflavans (demethylvestitol, vestitol and sativan) are also produced by L. hispidus. The synthesis of 5-, 6- and 8-methoxyvestitol is described. Preparation of the pterocarpan analogues of 6- and 8-methoxyvestitol has allowed the structures of two additional legume phytoalexins to be unequivocally confirmed.     

Isoflavan phytoalexins from Anthyllis,lotus and Tetragonolobus

Two previously unreported phytoalexins, 7,4′dihydroxy-2′-methoxy- and 7,2′,4′-trihydroxyisoflavan, have been isolated from the fungus-inoculated leaves of Anthyllis vulneraria and 5 Tetragonolobus species. Examination of Lotus corniculatus revealed the co-occurrence of the latter with the known isoflavans, vestitol and sativan. Only 7,2′4′-trihydroxyisoflavan and vestitol were produced by the closely related L. uliginosus.     

Astraciceran: a new isoflavan phytoalexin from Astragalus cicer

A new phytoalexin isolated from the fungus-inoculated leaflets of Astragalus cicer has been identified as 7-hydroxy-2′-methoxy-4′,5′-methylenedioxyisoflavan (astraciceran). The synthesis of astraciceran and its 3′,4′-methylenedioxy analogue is described.     

Tephrocarpin,a pterocarpan phytoalexin from Tephrosia bidwilli and a structure proposal for acanthocarpan

The isoflavonoids (-)-6aR; 11aR-maackiain, (-)-6aS; 11aS-pisatin and (-)-6aR; 11aR-4-methoxy- maackiain have been isolated as p     

Identification of the Erythrina phytoalexin cristacarpin and a note on the chirality of other 6a-hydroxypterocarpans

Cristacarpin, a new phytoalexin from Erythrina crista-galli is assigned the structure (?)-3,6a-dihydroxy-9-methoxy-10-γ,γ-dimethylallyl-cis-pterocarpan. It is accompanied by the known phytoalexins phaseollidin and demethylmedicarpin in this plant. Cristacarpin, phaseollidin and demethylmedicarpin were also obtained from E. sandwicensis and (together with isomedicarpin) from the related legume, Psophocarpus tetragonolobus. A compilation of selected optical rotation, NMR and conformational data for all known 6a-hydroxypterocarpans is presented and it is concluded that the previously assigned chiralities of neobanol, glyceollins I–IV and 3,6a,9-trihydroxypterocarpan should be reversed. Chirality assignments are made for a number of previously unassigned compounds.     

Fungal modification of pterocarpan phytoalexins from Melilotus alba and Trifolium pratense

Medicarpin (3-hydroxy-9-methoxypterocarpan), an isoflavonoid phytoalexin characteristic of sweetclover (Melilotus alba), is metabolised by three fungi, Botrytis cinerea, Colletotrichum lindemuthianum (race β) and C. coffeanum (isolates CCA and CCP) to afford products with decreased antifungal activity. Peterocarpan phytoalexins from red clover (Trifolium pratense) are similarly modified. A fourth organism, Helminthosporium carbonum apparently lacks this ability. Fungal-mediated tranformation principally involves hydroxylation, methylation and demethylation although ring fission has also been noted.     

Induction and identification of sativan and vestitol as two phytoalexins from Lotus corniculatus

Two phytoalexins, (-)-sativan, previously named sativin, [(-)-7-hydroxy-2′,4′-dimethoxyisoflavan], and (-)-vestitol, [(-)-7,2′-dihydroxy-4′-methoxyisoflavan], were induced by a spore suspension of Helminthosporium turcicum Pass. to accumulate in leaves of birdsfoot trefoil (Lotus corniculatus L.).     

3,6a-Dihydroxy-8,9-methylenedioxypterocarpan as a metabolite of pisatin produced by Fusarium solani f. sp. pisi

One of the fungal metabolites of pisatin has been identified as resulting from the demethylation of pisatin at position 3.     

Insect feeding deterrent activity of phytoalexin isoflavonoids

When incorporated into an agar-cellulose medium containing feeding stimulants, phytoalexin isoflavonoids from several legumes show feeding deterrent activity against larvae of the insect Costelytra zealandica and Heteronychus arator. The levels at which these compounds deter feeding are of the same order of magnitude as those at which they reduce fungal growth. The most active compound tested was phaseollin. These results suggest that phytoalexin isoflavonoids show a dual acitvity against insects and fungi.     

Isolation of a new isoflavan phytoalexin from two Lotus species

A phytoalexin isolated from the fungus-inoculated leaflets of Lotus angustissimus and L. edulis has been characterised as 5,7-dimethoxy-2′,4′-dihydroxyisoflavan (lotisoflavan). The total synthesis of lotisoflavan is described.     

Dolichins A and B,two pterocarpans from bacteria-treated leaves of Dolichos biflorus

Two minor isoflavonoids isolated from bacteria-inoculated leaves of Dolichos biflorus have been identified as the 6aR; 11aR; 2′S and 6aR; 11aR; 2′S isomers of 3,9-dihydroxy-10-2′-hydroxy-3′-methyl-3′-butenyl pterocarpan.     

Two novel stilbene-2-carboxylic acid phytoalexins from Cajanus cajan

Three phytoalexins were isolated from leaves of pigeon pea which had been challenged with Botrytis cinerea. One was identified as pinostrobin chalc     

Isoflavonoids of Mildbraedeodendron excelsa

The heartwood of Mildbraedeodendron excelsa has yielded five isoflavones and an ( ± )-isoflavanone. The structure of 7,4′-dihydroxy-6-methoxyisoflavone (glycetein) was confirmed by synthesis.