Junzo Shoji

Phenolic constituents of phellodendron amurense bark

Abstract Clycosides of (±)-5,5′-dimethoxylariciresinol, 2( p -hydroxy-phenyl)-ethanol and N -methylhigenamine were isolated from the dried bark of Phellodendron amurense , together with nine phenolic compounds.

Terpenoids of Alisma orientale rhizome and the crude drug alismatis rhizoma

Abstract From fresh rhizome of Alisma orientale, and the crude drug Alismatis rhizoma of Japanese and Chinese origins, 15 new terpenoids were isolated together with 11 known terpenoids and were characterized as follows: 11-deoxy, 13β,17β-epoxy and ll-deoxy-13β,17β-epoxy derivatives of alisols, alisol C, 16,23-oxidoalisol B, 25-O-methyl and 25-anhydro derivatives of alisol A, as well as eudesma-4(14)-en-1,6-diol, 10-O-methyl-alismoxide and 16(R)-(−)-kaurane-2,12-dione.

Oleanolic acid saponins from root-bark of Aralia elata.

Three new oleanolic acid glycosides, tarasaponins I-III, were isolated as their methyl esters from the root bark of Aralia elata together with four known glycosides, the methyl esters of chikusetsusaponins IVa, IV, 28-desglucosyl-chikusetsusaponin IV and pseudoginsenoside RT1. Tarasaponins I-III were characterized as oleanolic acid 3-O-[beta-D-glucopyranosyl(1-->3)][alpha-L-arabinofuranosyl(1-->4)[- beta-D-glucuronopyranoside, oleanolic acid 3-O-[beta-D-xylopyranosyl(1-->2)][beta-D-galactopyranosyl(1-->3)]-beta- D-glucuronopyranoside and beta-D-glucopyranosyl oleanolate 3-O-beta-D-galactopyranosyl(1-->3)-beta-D-glucuronopyranoside, respectively.

Studies on leguminous plants. Part XXXIV. Six New Triterpenoidal Glycosides Including Two New Sapogenols from Albizziae Cortex. V.

Six new triterpenoid glycosides called julibrosides A1-A4, B1 and C1 were isolated from Albizziae Cortex, the dried stem bark of Albizzia julibrissin Durazz. Their structures were determined based on spectral and chemical evidence. Julibrosides B1 and C1 had new sapogenols, designated julibrogenin B and C, respectively, while julibrosides A3 included N-acetyl-D-glucosamine as a sugar component.

Saponins from leaves of Acanthopanax sieboldianus

Two new triterpenoid saponins named sieboldianoside A and B were isolated from the leaves of Acanthopanax sieboldianus together with five known triterpenoid saponins, kalopanax-saponins A and B, saponin A, CP3, sapindoside B, and a known flavonol glycoside, kaempferol 3-O-rutinoside. On the basis of chemical and spectral evidence, the structures of the new saponins (sieboldianoside A and B) were concluded to be alpha-L-rhamnopyranosyl(1-->4)-beta-D-glucopyranosyl(1-->6)- beta-D-glucopyranosyl esters of hederagenin and oleanolic acid 3-O-beta-D- xylopyranosyl(1-->3)-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopy ranosides, respectively.

Konbamide, a novel peptide with calmoduiin antagonistic activity from the Okinawan marine sponge Theonella sp.

A novel peptide, konbamide 1, with calmodulin antagonistic activity has been isolated from the Okinawan marine sponge Theonella sp. and the structure elucidated to be a unique hexapeptide with an ureido bond on the basis of spectroscopic data, including two-dimensional NMR techniques and FAB MS–MS analysis (FAB = fast atom bombardment).

Steroidal glycosides from the subterranean parts of Liriope spicata var. prolifera

In a continuation of phytochemical studies on the underground organs of Liriope spicata var. prolifera, four new steroidal glycosides, lirioproliosides A-D, along with two known compounds, 25(S)-ruscogenin 1-O-[alpha-L-rhamnopyranosyl(1-->2)[beta-D-xylopyranosyl (1-->3)]-beta-D-fucopyranoside and ophiopogonin A, were identified. The structures of lirioproliosides A-D were established by a combination of spectroscopic and chemical methods as 25(S)-ruscogenin 1-O-[alpha-L-rhamnopyranosyl(1-->2)][beta-D-xylopyranosyl (1-->3)]-beta-D-fucopyranoside-3-O-alpha-L-rhamnopyranoside, 25(S)-ruscogenin 1-O-[3-O-acetyl-alpha-L-rhamnopyranosyl(1-->2)]-beta-D-fucopyranoside, 25(S)-ruscogenin (1-O-[2-O-acetyl-alpha-L-rhamnopyranosyl (1-->2)]-beta-D-fucopyranoside and ruscogenin (1-O-[2-O-acetyl-alpha-L-rhamnopyranosyl(1-->2)]-beta-D-fucopyranoside, respectively. Among these steroidal glycosides, ophiopogonin A and lirioprolioside B, and lirioproliosides C and D, were isolated as epimeric pairs.

Saponins can cause the agglutination of phospholipid vesicles.

The interaction of saponins with phospholipid vesicles was investigated by means of liposomal agglutination or a precipitation assay. Ginsenoside-Rc, which has an alpha-L-arabinofuranose residue at the non-reducing terminus, exhibited remarkable agglutinability toward egg yolk phosphatidylcholine vesicles, while other saponins lacking this characteristic sugar residue showed less or no agglutinability. The molar ratio of ginsenoside-Rc to egg phosphatidylcholine in the aggregates was estimated to be 0.4-0.5 by a precipitation assay using 14C-labeled egg phosphatidylcholine vesicles. The agglutination was inhibited by p-nitrophenyl alpha-L-arabinofuranoside but not by p-nitrophenyl beta-D-glucopyranoside or arabinogalactan. The results indicated that the alpha-L-arabinofuranose residue in ginsenoside-Rc should be important for the expression of the agglutinability. The agglutinability of ginsenoside-Rc toward lipid vesicles depended on both the polar head groups and fatty acyl chains of phospholipids. Egg yolk phosphatidylcholine vesicles were strongly agglutinated by ginsenoside-Rc, although sphingomyelin, phosphatidylethanolamine, phosphatidic acid and phosphatidylserine were less agglutinated. The agglutinability of ginsenoside-Rc was effective for phosphatidylcholines with short or unsaturated fatty acyl chains. The results suggested that the interaction of ginsenoside-Rc with phospholipid membranes should be affected not only by the chemical structure of the phospholipid but also by the membrane fluidity.

Achyranthosides A and B, novel cytotoxic saponins from Achyranthes fauriei root

Abstract Two new saponins, achyranthosides A and B, were isolated from Achyranthes fauriei root, and their structures were elucidated on the basis of chemical and physical evidences. Achyranthoside A methyl ester was found to have significant cytotoxic activity against human colon carcinoma and murine melanoma cells.

Lupane triterpenoid glycosyl esters from leaves of Acanthopanax divaricatus

Abstract Further investigation of the leaves of Acanthopanax divaricatus gave two analogues of chiisanoside, which is a lupane triterpenoid oligoglycosyl ester. The structures were established as 28- O -α- l -rhamnopyranosyl(1 → 4)-β- d -glucopyranosyl(1 → 6)β- d -glucopyranosyl esters of 1β,11α-dihydroxy-3-oxo-lup-20(29)-en-28-oic acid and 1( R ),11α,22α-trihydroxy-3,4-seco-lupa-4(23),20(29)-diene-3,28-dioic acid 3,11α-lactone based on chemical and spectroscopic evidence. in biosynthetic terms, one is the precursor of chiisanoside and the other is an oxygenated derivative chiisanoside.