Motoo Tori

Cyclic bis(bibenzyls) and related compounds from the liverworts Marchantia polymorpha and Marchantia palmata

Abstract From the methanol extract of the Indian liverwort Marchantia polymorpha , two new cyclic bis(bibenzyls), isomarchantin C and isoriccardin C, and a new phenanthrene derivative, 2-hydroxy-3,7-dimethoxyphenanthrene, were isolated together with the previously known cyclic bis(bibenzyls) marchantin A, C, D and E, riccardin C and perrottetin E and their structures were established by extensive 1 H NMR spectroscopic examination. Isomarchantin C, isoriccardin C, marchantin C and G, and riccardin C were also isolated from the Indian M. palmata . The two Marchantia species are chemically quite similar.

Chemical structures of macrocyclic bis(bibenzyls) isolated from liverworts (Hepaticae)

Liverworts (Hepaticae) produce a number of macrocyclic bis(bibenzyls) which show interesting biological activity and are of very valuable for the chemosystematic study of liverworts. The structural elucidation of these characteristic natural products are reviewed.

Immunosuppressive terpenoids from extracts of Tripterygium wilfordii

Abstract The clinically used extract (TΠ) of Tripterygium wilfordii Hook f. give 19 new compounds, including five kaurane diterpenes (1–5), one manoyl oxide diterpene (6), and one abietane diterpene (7), three ursene triterpenes (8, 9 and 15), six oleanane triterpenes (10–13, 16 and 19), and three friedelane triterpenes (14, 17 and 18), as well as 15 known compounds (20–34). Their structures were elucidated by spectroscopy and X-ray analysis. Based on the screening of isolated compounds and other compounds reported in previous papers [J. Nat. Prod. 62 (1999) 1522; J. Nat. Prod. (2001) in press; Phytochemistry 53 (2000) 805], we identified the main components that are responsible for the therapeutic effect of TΠ.

Prenyl bibenzyls from the liverworts Radula perrottetii and Radula complanata

Abstract A new dihydrobenzofuran and a new chromene derivatives have been isolated from the liverwort Radula perrottetii , together with the known 3,5-dihydroxy-2-(3-methyl-2-butenyl)bibenzyl, 2( R )-2-isopropenyl-6,7-dihydroxy-4-(2-phenylethyl)dihydrobenzofuran, 2,2-dimethyl-7-hydroxy-5-(2-phenylethyl)chromene, 3,5-dihydroxy-6-carbo-methoxy-2-(3-methyl-2-butenyl)bibenzyl, three bis(bibenzyls) and perrottetins E, F and G. The structures of the new compounds have been characterized as 2( R )-2-isopropenyl-6-hydroxy-4-(2-phenylethyl)dihydrobenzofuran and 2,2-dimethyl-7,8-dihydroxy-5-(2-phenylethyl)chromene by 1 H and 13 C NMR spectral analysis and synthesis. The structures of the previously reported chalcone and three prenyl bibenzyls, perrottetins A, B and C, and the other two bibenzyls, isolated from R. perrottetii are revised by analysis of their 1 H and 13 C NMR data, difference NOE experiments and synthesis of their derivatives. Radulanin L, a new bibenzyl with a dihydrooxepin skeleton was isolated from R. complanata together with 2- and 4-(3-methyl-2-butenyl)-3,5-dihydroxybibenzyls and its structure elucidated by comparison of 1 H and 13 C NMR spectral data with those of radulanins A and H. The structures of the previously reported radulanins A and H isolated from R. complanata are confirmed as correct by difference NOE. Some prenyl-containing bibenzyls showed 5-lipoxygenase and calmodulin in hibitory activity and vasopressin antagonist activity. R. perrottetii is a chemically isolated species in the Radulaceae.

Three dihydroisocoumarin glucosides from Hydrangea macrophylla subsp. serrata

Abstract Three new dihydroisocoumarin glucosides, macrophyllosides A, B and C were obtained from dry leaves of Hydrangea macrophylla subsp. serrata, together with the previously known hydrangenol 8-β-glucoside. Using NMR and CD techniques and some chemical transformation, the structures were elucidated as (3S)-3′,4′,5′-trimethoxyphenyl-8-β- D -glucopyranosyl dihydroisocoumarin, (3R and (3S)-3′,5′-dimethoxy-4′-hydroxyphenyl-8-β- D -glucopyranosyl dihydroisocoumarins. CD experiments indicated that hydrangenol 8-β-glucoside was the mixture of 3S- and 3R- stereoisomers.

Three novel dimethyl pyrroledicarboxylate, lycogarubins AC, from the myxomycetes lycogala epidendrum

Abstract Three novel dimethyl pyrroledicarboxylate, named lycogarubins AC have been isolated from the Myxomycetes Lycogala epidendrum. Their structures have been established by a combination of two dimension NMR spectroscopy, X-ray crystallographic analysis and chemical degradation. Lycogarubin C showed moderate anti-HSV-I virus activity.

Preparation of biologically active substances and animal and microbial metabolites from menthols, cineoles and kauranes

Abstract Six monoterpenoids, l-menthol, l-menthyl acetate, iso-menthol, neo-menthol, 1,4-cineole and 1,8-cineole and one diterpene hydrocarbon, ent-kaurene were oxidized by meta-chloroperbenzoic acid or dry ozone to give various hydroxylated products and their structures elucidated by NMR spectroscopy. Some hydroxylated menthols showed plant growth inhibitory and strong mosquito repellent activity. Among the hydroxylated cineoles, microbial and animal metabolites of cineoles were included. From ent-kauranes, a plant growth inhibitory diterpene alcohol, (−)-16α-hydroxy kaurane was obtained along with 16α-kauran-13α-ol.

Eremophilane-type sesquiterpenes from fresh rhizomes of Petasites japonicus

Abstract Ten new eremophilane-type sesquiterpene lactones, eremopetasitenins A1, A2, B1, B2, C1, C2, C3, D1, D2, and D3, sulphoxide bearing lactone, eremopetasinsulphoxide, and two methoxyl derivatives, as well as seven previously known sesquiterpenes have been isolated from fresh rhizomes of Petasites japonicus and their structures determined by spectroscopic techniques. Epoxyeremophilanolides, eremopetasitenins A1, A2, B1, and B2, are proposed to be important biogenetic intermediates.

Phenolic constituents of the liverwort: Four novel cyclic bisbibenzyl dimers from Blasia pusilla L

Abstract Four novel, cyclic, bisbibenzyl dimers (pusilatins A-D), six bibenzyl derivatives, apigenin 7-O-β- d -glucoside , shikimic acid and five orsellinic acid derivatives have been isolated from the methanolic extract of the liverwort Blasia pusilla L. and their structures characterized by a combination of spectral data, chemical modification and X-ray crystallographic analysis. The previously assigned structure of pusilatin D was revised. Pusilatins B and C showed DNA polymerase β inhibitory activity.

Total assignment of 1H and 13C NMR spectra of marchantins isolated from liverworts and its application to structure determination of two new macrocyclic bis(bibenzyls) from Plagiochasma intermedium and Riccardia multifida

Abstract 1 H and 13 C NMR spectra of five marchantins isolated from Marchantia species (Liverwort) have been completely assigned using NOE difference, 13 C- 1 H correlation and long-range proton selective decoupling (LSPD) spectra. The structures of two macrocyclic bis(bibenzyls) have been determined by use of this assignment.