Phytochemistry (v.65, #18)

Graphical abstracts (2521-2525).

Halogenated diterpenoids from the red alga Laurencia nipponica by Ekaterina G. Lyakhova; Anatoly I. Kalinovsky; Sophia A. Kolesnikova; Victor E. Vaskovsky; Valentin A. Stonik (2527-2532).
Two halogenated diterpenes, 15-bromoparguer-9(11)-ene-16-ol (11) and 15-bromoparguer-7-ene-16-ol (12), have been isolated from the red alga Laurencia nipponica. Their structures were elucidated by analysis of 1D and 2D NMR, mass spectra and molecular calculations.Chemical compositions of three collections of the red alga Laurencia nipponica from the western part of the Sea of Japan were studied. One of them contained a series of the previously known sesquiterpenoids. Another one gave C15 bromoallene ethers, predominantly. Finally, two new halogenated diterpenes, 15-bromoparguer-9(11)-ene-16-ol and 15-bromoparguer-7-ene-16-ol, were isolated from the third collection of the same species. Structures of these diterpenoids were established by 1D and 2D NMR (1H–1H COSY, DEPT, HMQC, HMBC and NOESY) along with molecular calculations for conformations having lowest energies and mass spectroscopy. Diversity and variability of halogenated secondary metabolites in L. nipponica were discussed.
Keywords: Laurencia nipponica; Rhodophyceae; Rhodomelaceae; Red alga; Diterpenoid; Halogenated metabolite; Chemical structure; Chemical diversity;

Clerodane-type diterpenoids from Nannoglottis ravida by Hai-Lin Qin; Zhi-Hong Li (2533-2537).
Clerodane-type diterpenoides, ravidin A and B, were isolated from the roots of Nannoglottis ravida, and their chemotaxonomical significance is discussed.Chemical investigation of the roots of Nannoglottis ravida resulted in the characterization of two 5α,10α-cis-clerodane-type diterpenoides, ravidin A and B. Their structures and stereochemistry were established by spectroscopic methods, including X-ray crystallographic diffraction analysis of ravidin A. Their significance in terms of the chemotaxonomy of Nannoglottis is discussed.
Keywords: Nannoglottis ravida; Compositae; Structural determination; Stereochemistry; Clerodane-type diterpenoids; Ravidin A and B;

Nor-ent-kaurane diterpenes and hydroxylactones from Antennaria geyeri and Anaphalis margaritacea by Ahmed A. Ahmed; Taha A. Hussein; Ahmed A. Mahmoud; Mohamed A. Farag; Paul W. Paré; Małgorzata Wojcińska; Joe Karchesy; Tom J. Mabry (2539-2543).
Antennaria geyeri afforded nor-ent-kaurane diterpenes with antibacterial activity. Anaphalis margaritacea afforded two hydroxy lactones. Structures were elucidated on the basis of 1D and 2D NMR analysis, IR and CIMS.In a study of Pacific Northwest plants of the Asteraceae family, a nor-ent-kaurane diterpene and a known diterpene, both displaying antibacterial activities, were isolated together with scopoletin and sitosterol-3-O-β-glucopyranoside from the aerial parts of Antennaria geyeri. Anaphalis margaritacea afforded two hydroxylactones. The structures were established by one and two dimensional NMR techniques, IR and CIMS.
Keywords: Antennaria geyeri; Anaphalis margaritacea; Asteraceae; nor-ent-kaurane; Diterpenes; Hydroxylactones; Antibacterial;

Two lanostane triterpenoids from Abies koreana by Hyun Jung Kim; Eun Hwa Choi; Ik-Soo Lee (2545-2549).
Lanostane-type triterpenoids were isolated from the root bark of Abies koreana, and their cytotoxicity properties were assessed. Their structures were elucidated based on spectroscopic analyses.Two lanostane-type triterpenoids, namely, 24(E)-3,4-seco-9βH-lanosta-4(28),7,24-triene-3,26-dioic acid and 24(E)-3-oxo-9βH-lanosta-7,24-dien-26-ol were isolated from the root bark of Abies koreana. Their structures were established based on spectroscopic analyses. Compound 2 exhibited marginal cytotoxicity against human tumor cell lines.
Keywords: Abies koreana; Pinaceae; Lanostanes; 24(E)-3,4-seco-9βH-lanosta-4(28),7,24-triene-3,26-dioic acid; 24(E)-3-oxo-9βH-lanosta-7,24-dien-26-ol; Cytotoxicity;

Dendrocyin: an isocucurbitacin with novel cyclic side chain from Dendrosicyos socotrana by Hosny A. Hussein; Osama B. Abdel-Halim; El-Sayed M. Marwan; Ali A. El-Gamal; Ramazy Mosana (2551-2556).
From the chloroform extract of Dendrosicyos socotrana Balf.f. stems, A new isocucurbitacin (Dendrocyin) with unusual cyclization in the side chain; 24β-ethoxy-20-25-epoxy-3α,16α-dihydroxy-9-methyl-19-norlanost-5(6) ene-2,11,22-trione has been isolated alongside isocucurbitacin R. Dendrosicyos socotrana Balf.f. is a unique species (Cucurbitaceae) native to Socotra island in the horn of Africa. From the chloroform extract of the stems, A new isocucurbitacin (Dendrocyin) with unusual cyclization in the side chain; 24β-ethoxy-20-25-epoxy-3α,16α-dihydroxy-9-methyl-19-norlanost-5(6) ene-2,11,22-trione has been isolated alongside isocucurbitacin R. Their structural configuration were established by usual spectroscopic (1H NMR, 13C NMR and DEPT) and two-dimensional NMR techniques (1H–1H Cosy, HMBC and HMQC).
Keywords: Dendrosicyos socotrana Balf.f.; Cucurbitaceae; Stems; Isocucurbitacins;

Terpenoids from Microliabum polymnioides by Oscar J. Díaz; Roberto Gil; Lázaro J. Novara; Virginia E. Sosa; Juana R. de la Fuente (2557-2560).
11αH,13-dihydrozaluzanin E (1), and a noreudesmanolide: 1 β-hydroxy-4-oxo-11βH-4-noreudesman-6,12-olide (2) were isolated and characterized from Microliabum polymnioides, together with related known sesquiterpenolides and the results used for chemotaxanomical classification.The phytochemical study of M. polymnioides led to the isolation of two sesquiterpene lactones namely: 11αH-dihydrozaluzanin E and 1β-hydroxy-4-oxo-11βH-4-noreudesman-6,12-olide. Their structures were determined by spectroscopic methods. The relative stereochemistry was established by a combination of coupling constant analysis, NOESY correlations and molecular modeling. Three related known sesquiterpene lactones were also identified, and these data were used for chemotaxonomical purposes.
Keywords: Microliabum; Liabum; Liabeae; Asteraceae; Modified guaianolide; Noreudesmanolide; Chemotaxonomy;

Allanxanthone B, a polyisoprenylated xanthone from the stem bark of Allanblackia monticola Staner L.C by Anatole G.B. Azebaze; Michèle Meyer; Bernard Bodo; Augustin E. Nkengfack (2561-2564).
A polyisoprenylated xanthone, named allanxanthone B, was isolated from the stem bark of Allanbackia monticola, together with five known compounds. The antimicrobial activity of some of these compounds are also reported.In addition to five known compounds including three xanthones, tovophyllin A, rubraxanthone and garciniafuran, one pentacyclic triterpene, lupeol and one phytosterol, stigmasterol, a polyisoprenylated xanthone named allanxanthone B was isolated from the stem bark of Allanblackia monticola. The structure of the new compound was assigned as 2-geranyl-1,3,6-trihydroxy-2′,2′-dimethyl[5′,6′:7,8]xanthone by means of spectroscopic analysis. The antimicrobial activities of some of these compounds against a range of micro-organisms are also reported.
Keywords: Allanblackia monticola; Guttiferae; Allanxanthone B; Xanthones; Lupeol; Stigmasterol; Antimicrobial activities;

Alkaloidal constituents of Mucuna pruriens seeds by Laxminarain Misra; Hildebert Wagner (2565-2567).
Four tetrahydroisoquinoline alkaloids have been isolated from Mucuna pruriens seeds for the first time, out of which two are new. Their structures have been established by spectroscopic methods.The seeds of Mucuna pruriens (L.) DC. after chemical analysis afforded four tetrahydroisoquinoline alkaloids which have been isolated for the first time from M. pruriens. Out of them, two are new whose structures have been elucidated by spectroscopic methods.
Keywords: Mucuna pruriens (L.) DC. syn. M. prurita Hk.; Papilionaceae; Seeds; Amino acids; Alkaloids; Tetrahydroisoquinoline; Antiparkinson; Aphrodisiac;

Azaphilone pigments from a yellow mutant of the fungus Monascus kaoliang by Suchada Jongrungruangchok; Prasat Kittakoop; Busaba Yongsmith; Rapepol Bavovada; Somboon Tanasupawat; Nattapat Lartpornmatulee; Yodhathai Thebtaranonth (2569-2575).
Azaphilone pigments, monascusones A (1) and B (2), were isolated from the extract of the fungus Monascus kaoliang grown on rice.Azaphilone pigments, monascusones A (1) and B (2), together with two known azaphilones, monascin (3) and FK17-P2b2 (4), were isolated from the CH2Cl2 extract of a yellow mutant of the fungus M. kaoliang grown on rice. Structures of the isolated compounds were elucidated by analyses of spectroscopic data. Monascusone A (1), the major metabolite of M. kaoliang, showed no antimalarial (against Plasmodium falciparum), antitubercular (against Mycobacterium tuberculosis H37Ra), and antifungal (toward Candida albicans) activities. Compound 1 exhibited no cytotoxicity against BC (breast cancer) and KB (human epidermoid carcinoma of cavity) cell lines.
Keywords: Monascus kaoliang; Azaphilone pigments; Monascusone A; Monascusone B; Food colorant;

Diterpenoid glucosides from Salvia greggii by Nobuo Kawahara; Toru Tamura; Mayumi Inoue; Tomoo Hosoe; Ken-ichi Kawai; Setsuko Sekita; Motoyoshi Satake; Yukihiro Goda (2577-2581).
Four diterpenoid glucosides, designated as salvigresides A–D (14), were isolated from the aerial parts of Salvia greggii, with their structures confirmed by spectroscopic and chemical analyses.The structure of four diterpenoid glucosides, designated as salvigresides A–D (14), isolated from the aerial parts of Salvia greggii, have been confirmed by spectroscopic and chemical investigation.
Keywords: Salvigreside; Salvia greggii; Labiatae; Autumn sage; Diterpenoid glucoside;

Bioactivity guided isolation of antifungal compounds from the liverwort Bazzania trilobata (L.) S.F. Gray by Jochen M. Scher; John-Bryan Speakman; Josef Zapp; Hans Becker (2583-2588).
Bioautography on thin-layer chromatograms was used to isolate six antifungal sesquiterpenes and three bisbibenzyls from Bazzania trilobata. Their antifungal activities were compared by microtiter plate tests. Furthermore gymnomitr-8(12)-en-4-one and the new coumarin 7,8-dihydroxy-coumarin-7-O-β-d-glucuronide were isolated.A dichloromethane and a methanol extract of the liverwort Bazzania trilobata showed antifungal activity against the phytopathogenic fungi Botrytis cinerea, Cladosporium cucumerinum, Phythophthora infestans, Pyricularia oryzae and Septoria tritici. Bioautography on thin-layer chromatograms was used to isolate six antifungal sesquiterpenes: 5- and 7-hydroxycalamenene, drimenol, drimenal, viridiflorol, gymnomitrol and three bisbibenzyls: 6,8-dichloroisoplagiochin C, isoplagiochin D and 6-chloroisoplagiochin D. Furthermore we report the isolation of gymnomitr-8(12)-en-4-one and the new coumarin 7,8-dihydroxycoumarin-7-O-β-d-glucuronide. Their structures have been elucidated based on extensive NMR spectral evidence.
Keywords: Bazzania trilobata; Hepaticae; Liverwort; Antifungal; Bioautography;

Phloroglucinol derivatives from Mallotus pallidus by Butsarakham Supudompol; Kittisak Likhitwitayawuid; Peter J. Houghton (2589-2594).
From the leaves of Mallotus pallidus were isolated five phloroglucinol derivatives, namely pallidusol, dehydropallidusol, pallidol, mallopallidol and homomallopallidol. Their structures were determined by means of spectroscopic methods of analysis.From the leaves of Mallotus pallidus were isolated five phloroglucinol derivatives, namely pallidusol, dehydropallidusol, pallidol, mallopallidol and homomallopallidol. Their structures were determined by means of spectroscopic methods of analysis.
Keywords: Mallotus pallidus; Euphorbiaceae; Phloroglucinol;

Sulfonated xanthones from Hypericum sampsonii by Di Hong; Feng Yin; Li-Hong Hu; Ping Lu (2595-2598).
Two xanthones 1 and 2, together with nine known compounds were obtained from the whole plant of Hypericum sampsonii. This is the first report of sulfonated xanthonoids. Compounds 1 and 2 exhibited significant cytotoxicity to P388 cancer cell line.Xanthones, 1,3-dihydroxy-5-methoxyxanthone-4-sulfonate and 1,3-dihydroxy-5-O-β-d-glycopyranosylxanthone-4-sulfonate, together with nine known compounds were obtained from H. sampsonii. This is the first report of sulfonated xanthonoids. Furthermore, compounds 1 and 2 exhibited significant cytotoxicity against the P388 cancer cell line.
Keywords: Hypericum sampsonii; Guttiferae; Xanthonoid sulfonates; Cytotoxicity;

Aliphatic acid amides of the fruits of Zanthoxylum piperitum by Tsutomu Hatano; Kazutoshi Inada; Tomo-omi Ogawa; Hideyuki Ito; Takashi Yoshida (2599-2604).
Six aliphatic acid amides, ZP-amides A–F, were isolated from the pericarp of Zanthoxylum peperitum fruits.Six aliphatic acid amides (16) were isolated from the pericarp of Zanthoxylum piperitum fruits. MS and NMR spectroscopic investigation revealed that these compounds have a ketone and/or hydroxyl group(s) in the unsaturated aliphatic acid moiety of the structure of the amides. Combinations 34 and 56 are stereoisomers in terms of the relative configurations of their two asymmetric carbons.
Keywords: Zanthoxylum piperitum; Rutaceae; Fruit; Aliphatic acid amide; Stereoisomer;

The tornabeatins, four tetrahydro-2-furanone derivatives from the lichenized ascomycete Tornabea scutellifera (With.) J.R. Laundon by Tomáš Řezanka; Marina Temina; Lumı́r Hanuš; Valery M. Dembitsky (2605-2612).
Tornabeatins A, B, C and D, have been isolated as new natural products from the lichen Tornabea scutellifera, and their structures were elucidated using spectral data.Tornabeatins A, B, C and D, have been isolated as new natural products from the lichenized ascomycete Tornabea scutellifera, and their structures elucidated using UV, IR, MS, 1D and 2D NMR spectral data and chemical degradation.
Keywords: Tornabea scutellifera; Tornabeatins; Lichenized ascomycete; Tetrahydro-2-furanones;

Triterpenoidal glycosides from Justicia betonica by Tripetch Kanchanapoom; Pawadee Noiarsa; Somsak Ruchirawat; Ryoji Kasai; Hideaki Otsuka (2613-2618).
Four triterpenoidal glycosides, justiciosides A–D, were isolated from the aerial portion of Justicia betonica.From the aerial portion of Justicia betonica L., four triterpenoidal glycosides (justiciosides A–D) were isolated. Their structures were established through chemical and NMR spectroscopic analyses as olean-12-ene-1β,3β,11α,28-tetraol 28-O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside, olean-12-ene-1β,3β,11α,28-tetraol 28-O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside, 11α-methoxy-olean-12-ene-1β,3β,28-triol 28-O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside, 11α-methoxy-olean-12-ene-1β,3β,28-triol 28-O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside, respectively.
Keywords: Justicia betonica; Acanthaceae; Justiciosides A–D; Triterpenoidal glycoside; Olean-12-ene-1β; 3β; 11α; 28-tetraol; 11α-Methoxy-olean-12-ene-1β, 3β;

Glycosides from Phlomis lunariifolia by İhsan Çalış; Hasan Kırmızıbekmez (2619-2625).
A new aliphatic alcohol glycoside, lunaroside (1), a new phenylethanoid glycoside, lunariifolioside (2) and a new flavon glycoside, luteolin 7-O-[4-O-acetyl-α-rhamnopyranosyl-(1 → 2)]-β-glucuronopyranoside (3) were isolated from Phlomis lunariifolia. The structures were established by 1D and 2D NMR techniques.An aliphatic alcohol glycoside, lunaroside 1-octen-3-yl O-β-apiofuranosyl-(1 → 6)-O-[β-glucopyranosyl-(1 → 2)]-β-glucopyranoside, a phenylethanoid glycoside, lunariifolioside 2-(3,4-dihydroxyphenyl)ethyl O-β-apiofuranosyl-(1 → 6)-O-[O-β-apiofuranosyl-(1 → 4)-α-rhamnopyranosyl-(1 → 3)]-4-O-(E)-caffeoyl-β-glucopyranoside and a flavone glycoside, luteolin 7-O-[4-O-acetyl-α-rhamnopyranosyl-(1 → 2)]-β-glucuronopyranoside, were isolated from the aerial parts of Phlomis lunariifolia, in addition to 15 known glycosides. Their structures were elucidated on the basis of extensive 1D and 2D NMR spectroscopic interpretation and chemical degradation.
Keywords: Phlomis lunariifolia; Lamiaceae; Aliphatic alcohol glycoside; Lunaroside, Phenylethanoid glycoside; Lunariifolioside; Flavone glycoside;