Trechonolide A,a new withanolide type from Trechonaetes laciniata

The structure of a new withanolide type isolated from Trechonaetes laciniata, having a hemiacetal ring system and a 5-member ring lactone has been elucidated by X-ray analysis as (23R)-5β,6β-epoxy-12β,17β-dihydroxy-1-oxo-12,22-hemiacetal-ergosta-2,24-dien-23,26-olide (trechonolide A). A second compound (trechonolide B) having at C-12 a β-methoxy group, has also been isolated and assumed to be an artifact since, by heating trechonolide A in methanol with a trace of acid, the methoxy derivative was produced.     

Arvensoside A and B,triterpenoid saponins from Calendula arvensis

Two new triterpenoid glycosides from the aerial parts of Calendula arvensis were identified as oleanolic acid-28-O-β-D-glucopyranoside-3-β-O-(O-β-D-galactopyranosyl(1 → 3)-β-D-glucopyranoside) and oleanolic acid 3-β-O-(O-β-D-galactopyranosyl(1 → 3)-β-D-glucopyranoside) by FAB, FAB MIKE mass spectrometry and ¹³C NMR spectroscopy.     

A furostanol glycoside from Helleborus macranthus

From the roots and rhizomes of Helleborus macranthus a new glycoside, macranthoside I, has been isolated and shown to have the structure 25(27)-dehydro-5β-furostan-3β,22,26-triol-3-O-β-d-glucopyranosyl(1 → 6)-β-d-glucopyranoside, 26-O-β-d-glucopyranoside.     

Costusoside-I and costusoside-J,two new furostanol saponins from the seeds of Costus speciosus

The structure of costusoside I and costusoside J have been established as 3-O-{β-d-glucopyranosyl (1 → 2)-α-l-rhamnopyranosyl (1 → 2) [α-l-rhamnopyranosyl (1 → 4)]-β-d-glucopyranosyl}-26-O-(β-d-glucopyranosyl)-22α-methoxy 25 R)-furost-5-en-3β, 26-diol and its 22-hydroxy compound respectively, isolated fron the seeds of Costus speciosus.     

The synthesis of afzelin,paeonoside and kaempferol 3-O-β-rutinoside

The structure of afzelin (kaempferol 3-O-α-l-rhamnopyranoside) and paeonoside (kaempferol 3,7-bis-O-β-d-glucopyranoside) has been confirmed by total synthesis. Synthetic kaempferol 3-O-β-rutinoside had a mp of 190–192° suggesting that those natural kaempferol 3-O-rhamnoglucosides which melt in the same range are also 3-O-β-rutinosides.     

Chlorantholides A–F,eudesmane-type sesquiterpene lactones from Chloranthus elatior

Six eudesmane-type sesquiterpene lactones, named chlorantholides A–F, were isolated from the ethanol extract of Chloranthus elatior (Chloranthaceae) together with 12 known compounds. Their structures were elucidated on the basis of extensive spectroscopic analysis, and their absolute configurations were studied by the CD exciton chirality method. The structure of a recently reported eudesmanolide from Chloranthus anhuiensis: 8β-hydroxy-1-oxoeudesma-3,7(11)-dien-12,8-olide, was also revised as 8β-hydroxy-2-oxoeudesma-3,7(11)-dien-12,8-olide (chlorantholide D).     

Tenasogenin,a pregnane ester from Marsdenia tenacissima

A new polyhydroxy pregnane ester named tenasogenin was isolated from the seeds of Marsdenia tenacissima. On the basis of chemical and spectroscopic evidence and identification of its hydrolysis products, its structure has been established as 11α-O-β,β-dimethylacryloyl-3β,12β,14β,20R-tetrahydroxypregn-5-ene.     

Dunawithanines A and B,the first withanolide glycosides from Dunalia australis

Withanolide D, 7β-acetoxy-withanolide D and two new withanolide glycosides, named dunawithanines A and B, were isolated from Dunalia australis. From physical data and chemical transformations, the structures of the new compounds were determined as (20R,22R-O(3)-[2′,3′-di-O-(β-D-glucopyranosyl)-β-D-glucopyranosyl]-3β,20-dihydroxy-1α-acetoxy-witha-5,24-dienolide and the corresponding O(3)-[β-D-glucopyranosyl(1′ → x)-β-D- glucopyranosyl] compound, representing the first withanolide glycosides found in the plant kingdom.     

A furostanol glucuronide from Solanum lyratum

A new furostanol glucuronide and three known glycosides, SL-O, aspidistrin and methyl proto-aspidistrin, were isolated from the fresh immature berries of Solanum lyratum. The structure of the new compound was characterized as 26-O-β-D-glucopyranosyl-(22ξ,25R-3β,22,26-trihydroxyfurost-5-ene 3-O-α-L-rhamnopyranosyl-(1 → 2)-[β-D-glucopyranosyl-(1 → 3)]-β-D-glucuronopyranoside.     

Grayanoside D,A diterpene glucoside from Leucothoe Grayana

A new diterpenoid glucoside, grayanoside D, has been isolated from Leucothoe grayana. Its structure was elucidated by chemical and spectroscopic means and by correlation with grayanotoxin-XV to be 3-O-(β-D-glucopyranosyl)-(10S)-dihydrograyanotoxin-XV.     

Glochidioside,a triterpene glycoside from Glochidion heyneanum

A new triterpenoid glycoside, glochidioside, has been isolated from Glochidion heyneanum. Its structure has been established as 3β[(O-β-D-glucopyranosyl-(1 → 3)-O-α-L-arabinopyranosyl)oxy]-16β-benzoyloxy-olean-12-ene-21β,23,28-trio     

A furan-2-carbonyl C-glucoside and an alkyl glucoside from the parasitic plant,Dendrophthoe pentandra

A new furan-2-carbonyl C-(6′-O-galloyl)-β-glucopyranoside (scleropentaside F, 1) and a new alkyl glucoside [butane-2,3-diol 2-(6′-O-galloyl)-O-β-glucopyranoside, 2] were isolated from the entire hemi-parasitic plant, Dendrophthoe pentandra growing on Tectona grandis together with ten known compounds including, benzyl-O-β-d-glucopyranoside (3), benzyl-O-α-l-rhamnopyranosyl-(1 → 6)-β-d-glucopyranoside (4), benzyl-O-β-d-apiofuranosyl-(1 → 6)-β-d-glucopyranoside (5), methyl gallate 3-O-β-d-glucopyranoside (6), methyl gallate 3-O-(6′-O-galloyl)-β-d-glucopyranoside (7), (+)-catechin (8), procyanidin B-1 (9) and procyanidin B-3 (10), bridelionoside A (11), and kiwiionoside (12). In addition, compounds 1, 3–9 were isolated from this species growing on the different host, Mangifera indica. The structure elucidations were based on physical data and spectroscopic evidence including 1D and 2D experiments.     

Beesioside III,a cyclolanostanol xyloside from the rhizomes of Beesia calthaefolia and Souliea vaginata

The chemical constituents of Beesia calthaefolia and Souliea vaginata were examined. From the rhizomes of B. calthaefolia, four new 9,19-cyclolanostanol xylosides, named beesiosides I–IV were isolated. Beesiosides 111 and IV were found also in the rhizomes of S. vaginata. On the basis of chemical and spectral evidence the structure of beesioside III was established as 15α-acetoxy-20ξ₁,24ξ₂-epoxy-9,19-cyclolanostane-3β,12β,16β,25-tetraol-3-O-β-D-xylopyranoside.     

Leptocarpin and 17,18-dihydroleptocarpin,two new heliangolides from Leptocarpha rivularis

The isolation and structure determination of two new sesquiterpene lactones of the heliangolide type, leptocarpin and 17,18-dihydroleptocarpin from Leptocarpha rivularis, are described. The structure of leptocarpin was established as the 8β-angeloyl ester of 3β,8β-dihydroxy germacra-4,11(13)-dien- 1(10)-oxido-6α,12-olide. The second component was the 17,18-dihydro derivative of leptocarpin.     

Entada saponin-III,a saponin isolated from the bark of Entada phaseoloides

The structure of Entada saponin (ES)-III, one of the main saponins of Entada phaseoloides bark, was established to be 3-O-[β-d-xylopyranosyl (1 → 2)-α-l-arabinopyranosyl (1 → 6)] [β-l-glucopyranosyl (1 → 4)]-2-acetamido-2-deoxy-β-l-glucopyranosyl-28-O-[β-l-apiofuranosyl (1 → 3)-β-d-xylopyranosyl (1 → 2)] [(2-O-acetoxyl)-β-d-glucopyranosyl-(1 → 4)] (6 − O(R) (−)2,6-dimethyl-2-trans-2,7-octadienoyl)-β-d-glucopyranosyl echinocystic acid.     

Arjunolitin,a triterpene glycoside fromTerminalia arjuna

Arjunolic acid diglycoside, which we have named arjunolitin, has earlier been reported fromTerminalia arjuna. Its structure has now been established as 3-O-β-d-glycopyranosyl 2α,3β-23-tri-hydroxyolean-12-en-28-oic acid 28-O-β-d-glucopyranoside by chemical and spectral data.     

Flavescin: A new 1-ketopolyhydroxypregnene from Marsdenia flavescens

A new polyhydroxy-1-ketosteroid, flavescin, was isolated from Marsdenia flavescens A. Cunn. Its structure was elucidated as 12-O-acetyl-3β,8β,12β,14β-20-pentahydroxy-Δ⁵- pregnene-1-one.     

Isoteuflidin,a neo-clerodane diterpenoid from Teucrium chamaedrys,and revised structures of teucrins F and G

A new neo-clerodane diterpenoid, isoteuflidin, was isolated from the aerial part of Teucrium chamaedrys. Its structure, 15,16-epoxy-3β-hydroxy-19     

Cissogenin,a pregnane genin from Marsdenia tenacissima

A new polyhydroxy pregnane designated as cissogenin has been isolated from the seeds of Marsdenia tenacissima. Its structure has been established as 3β,11α,12β,14β,20 S-pentahydroxy-pregn-5-ene.     

Immunochemical studies on blood groups: The internal structure and immunological properties of water-soluble human blood group A substance studied by Smith degradation,liberation, and fractionation of oligosaccharides and reaction with lectins

Carbohydrate structures in the interior of a blood group A active substance (MSS) were exposed by one and by two Smith degradations. Reactivities of the original glycoprotein and its Smith degraded products with 13 different lectins and with anti-I Ma were studied by quantitative precipitin assay. MSS and its first Smith degraded product completely precipitated Ricinus communis hemagglutinin with five times less of the first Smith degraded glycoprotein being required for 50% precipitation. The second Smith degraded material precipitated only 90% of the lectin. MSS did not precipitate peanut lectin, whereas its first and second Smith degraded products completely precipitated the lectin. The first Smith degraded glycoprotein also reacted well with Wistaria floribunda, Maclura pomifera, Bauhinia purpurea alba, and Geodia lectins indicating that its carbohydrate moiety could contain dGalNAc, dGalβ1 → 3dGalNAc, dGalβ1 → 4dGlcNAc, dGalβ1 → 3dGlcNAcβ1 → 3dGal and/or dGalβ1 → 4dGlcNAcβ1 → 6dGal and/or dGalβ1 → 4dGlcNAcβ1 → 6dGalNAc determinants at nonreducing ends. The second Smith degraded material precipitated well with Ricinus communis hemagglutinin, Arachis hypogaea, Geodia cydonium, Maclura pomifera, and Helix pomatia lectins showing that dGalNAc, dGalβ1 → 3dGalNAc, dGalβ1 → 4dGlcNAc residues at terminal nonreducing ends could be involved. Monoclonal anti-I Ma (group 1) serum reacted strongly with the first Smith degraded product indicating large numbers of anti-I Ma determinants, dGalβ1 → 4dGlcNAcβ1 → d 6dGal and/or dGalβ1 → 4dGlcNAcβ1 → 6dGalNAc at nonreducing ends. The comparable activities of the native and Smith degraded products with wheat germ lectin indicate capacity to react with DGlcNAc residues at nonreducing ends and/or at positions in the interior of the chain. The totality of lectin reactivities indicates heterogeneity of the carbohydrate side chains. Oligosaccharides with ³H at their reducing ends released from the protein core of the first and second Smith degraded products were obtained by treatment with 0.05 m NaOH and 1 M NaB³H₄ at 50 °C for 16 h (Carlson degradation). The liberated reduced oligosaccharides were fractionated by dialysis, followed by retardion, Bio-Gel P-2, P-4, and P-6 columns. They were further purified on charcoal-celite columns, and by preparative paper chromatography and high-pressure liquid chromatography. Their distribution by size was estimated by the yields on dialysis, Bio-Gel P-2, and Bio-Gel P-6 chromatography, and from the radioactivity of the reduced sugars. Of the oligosaccharide fractions from the first Smith degraded product, about 77% of the carbohydrate side chain residues contained from 1 to 6 sugars, 13% from 7 to perhaps 12 sugars, and 10% was nondialyzable (polysaccharides and glycopeptide fragments). Of the second Smith degraded product, approximately 82% of carbohydrate residues had from 1 to 6 sugars, 14% from 7 to perhaps 20 sugars and 4% was nondialyzable. The biological activity profile of the two Smith degraded products together with the size distributions of the oligosaccharides indicated that their carbohydrate side chains, comprised a heterogeneous population ranging in size from 1 to about 12 sugars. When most of these chains that are shorter than hexasaccharides are fully characterized it may be possible to reconstruct the overall structure of the carbohydrate moiety of the blood group substances and account for their biological activities.