Structure of monardaein,a bis-malonylated anthocyanin isolated from golden balm, monarda didyma

Structure of monardaein was determined to be 3-0-(6-0-$\text{trans}$-p-coumaryl-β-D-glucopyranosyl)-5-O- (4,6-di-O-malonyl-β-D-glucopyranosyl) pelargonidin (1).     

27-Nor-triterpenoid saponins from Adina rubella

Three new 27-nor-triterpenoid saponias named rubenorside A (1),rubenorside B(2) and rubenorside C (3) were isolated from the roots of Adina rubella.Their structures were characienzed as pyrocincholic acid 3β-O-α-L-rhamnopyranosyl(28→1 )-β-D-glucopyranosyl ester (1),pyrocinchohe acid 3β-O-β-D-glucopyranosyl(1→2)-β-D-fucopyranosyl(28→1)-β-D-glucopyranosyl(1→6)-β-D-glico-pyranosyl ester (2) and pyrocincholic acid 3β-O-β-D-glucopyranosyl(1→2)-β-D-glucopyranosyl(28→1)β-D-glucopyranosyl(1→6)-β-D-glucopyranosyl ester () by spectral methods,especially 2D NMR experiments.     

Structure of cinerarin, a tetra-acylated anthocyanin isolated from the blue garden cineraria,

Structure of cinerarin is determined to be 3-0-(6-0-malonyl-β-D-glucopyranosyl)-7-0-(6-0-(4-0-(6-0-caffeyl-β-D-glucopyranosyl)caffeyl)-β-D-glucopyranosyl)-3′-0-(6-0-caffeyl-β-D-glucopyranosyl)delphinidin.     

Synthesis of polysaccharides. Glucorhamnan

The regular heteropolysaccharide glucorhamnan

was obtained by polycondensation of 3-0-acetyl-4-0-(2,3,4-tri-0-acetyl-6-0-trityl-β-D-glucopyranosyl)-1,2-0-(1-exo-cyanoethylidene)-β-L-rhamnopyranose catalysed with triphenylmethylium perchlorate.     

Synthesis of Four Spacer-Containing Trisaccharides with the 4-0-(β-L-Rhamnopyranosyl)-D-glucopyranose Unit in Common,Representing Fragments of Capsular Polysaccharides from Streptococcus Pneumoniae Types 2, 7F, 22F,and 23F

Abstract

The synthesis is reported of 3-aminopropyl 3-O-[4-O(β-L-rhamnopyranosyl)-β-D-glucopyranosyl]-α-L-rhamnopyranoside (34), 3-aminopropyl 2-acetamido-3-O-[4-0-(β-L-rhamnopyranosyl)-β-D-glucopyranosyl]-2-deoxy-β-D-galactopyranoside (37), 3-aminopropyl 3-O-[4-O-(β-L-rhamnopyranosyl)-α-D-glucopyranosyl]-α-D-galactofuranoside (41), and 3-aminopropyl 4-O-[4-O-(β-L-rhamnopyranosyl)-β-D-glucopyranosyl]-β-D-galactopyranoside (45). These are spacer-containing fragments of the capsular polysaccharides of Streptococcus pneumoniae type 2, 7F, 22F, and 23F, respectively, which are constituents of Pneumovax^© 23. 2,3,4-Tri-O-benzyl-α-L-rhamnopyranosyl bromide was coupled to l,6-anhydro-2,3-di-(O-benzyl-β-D-glucopyranose (3). Opening of the anhydro ring, removal of AcO-1, and imidation of l,6-anhydro-2,3-di- O-benzyl-4-O-(2,3,4-tri-O-benzyl-β-L-rhamnopyranosyl)-β-D-glucopyranose (4β) afforded 6-O-acetyl-2,3-di-O-ben-zyl-4-O-(2,3,4-tri- O-benzyl-β-L-rhamnopyranosyl)-αβ-D-glucopyranosyl trichloroacet-imidate (7αβ). Condensation of 7αβ with 3-N-benzyloxycarbonylaminopropyl 2-O-ben-zyl-5,6-O-isopropylidene-α-D-galactofuranoside (26), followed by deprotection gave 41 Opening of the anhydro ring of 4 p followed by debenzylation, acerylauon, removal of AcO-1, and imidation yielded 2,3,6-tri-(9-aceryl-4-O-(2,3,4-tri-0-acetyl-P-L-rharnnopyran-.-osyl)-α-D-glucopyranosyl trichloroacetimidate (11). Condensation of 11 with 3-N-bcn-zyloxycarbonylaminopropyl 2,4-di-O-benzyl-α-L-rhamnopyranoside (18), with 3-N-bcn-zyloxycarbonylaminopropyl 2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-galactopyran-oside (21), or with 3-N -benzyloxycarbonylaminopropyl 2-O-acetyl-3-O-allyl-6-O-benzyl-β-D-galactopyranoside (31), followed by deprotection afforded 34, 37, and 45, respectively.     

Three new triterpenoid saponins from Dianthus superbus

Three new triterpenoid saponins (1-3) were isolated from the dried aerial parts of Dianthus superbus L. (Caryophyllaceae). Their structures were established as 3-O-β-D-glucopyranosyl gypsogenic acid 28-O-[β-D-6-O-((3S)-3-hydroxyl-3-methylglutaryl)glucopyranosyl(1→6)]-β-D-glucopyranoside (1), 3-O-β-D-glucopyranosyl gypsogenic acid 28-O-[β-D-glucopyranosyl(1→3)][β-D-6-O-((3S)-hydroxyl-3-methylglutaryl)glucopyranosyl(1→6)]-β-D-glucopyranoside (2), 3-O-α-L-arabinopyranosyl-3β,16α-dihydroxyolean-12-en-23,28-dioic acid 28-O-[β-D-glucopyranosyl-(1→6)]-β-D-glucopyranoside (3), on the basis of various spectroscopic analyses and chemical degradations.     

The structure of thelenotosides A and B from the holothurianThelenota ananas

Two new triterpene tetraosides — thelenotosides A and B — have been obtained from the holothurianThelenota ananas. Their complete structures have been determined as 23(S)-acetoxy-3β-[0-(3-0-methyl-β-D-glucopyranosyl)-(1→3)-0-β-D-xylopyranosyl-(1→4)-0-β-D-quinovopyranosyl-(1→2)-β-D-xylopyranosyloxy]holost-7-ene (and 23(S)-acetoxy-3β-[0-(3-0-methyl-β-D-glucopyranosyl)-(1→3)-0-β-D-xylopyranosyl-(1→4)-0-β-D-glucopyranosyl-(1→2)-β-D-xylopyranosyloxy]holost-7-ene, respectively.     

Structural determination of two new triterpenoid saponins acylated with monoterpenic acid from Gymnocladus chinensis Baill

Two new triterpenoid saponins acylated with monoterpenic acid, 2β,23-dihydroxy-3-O-α-L-rhamnopyranosyl-21-O-{(6S)-2-trans-2,6-dimethyl-6-O-[3-O-(β-D-glucopyranosyl)-4-O-(2-methylbutanoyl)-β-L-arabinopyranosyl]-2,7-octadienoyl)-acacic acid 28-O-β-D-xylopyranosyl-(1?→?3)-β-D-xylopyranosyl-(1?→?4)-[β-D-glucopyranosyl-(1?→?3)]-α-L-rhamnopyranosyl-(1?→?2)-[α-L-rhamnopyranosyl-(1?→?6)]-β-D-glucopyranosyl ester and 2β,23-dihydroxy-3-O-α-L-rhamnopyranosyl-21-O-{(6S)-2-trans-2,6-dimethyl-6-O-[4-O-((6S)-2-trans-2,6-dimethyl-6-O-(β-L-arabinopyranosyl)-2,7-octadienoyl)]-β-L-arabinopyranosyl]-2,7-octadienoyl}-acacic acid 28-O-β-D-xylopyranosyl-(1?→?3)-β-D-xylopyranosyl-(1?→?4)-[β-D-glucopyranosyl-(1?→?3)]-α-L-rhamnopyranosyl-(1?→?2)-[α-L-rhamnopyranosyl-(1?→?6)]-β-D-glucopyranosyl ester were isolated from the fruit of Gymnocladus chinensis Baill. and the structural elucidation of both the compounds was accomplished by extensive studies of their spectroscopic (1D and 2D NMR, TOF-MS, QFT-MS) and chemical methods.     

Heavenly blue anthocyanin II trans-4-0-(6-0-(trans-3-0-(β -d-glucopyranosyl)caffeyl)-β-d-glucopyranosyl)- caffeic acid,a novel component in heavenly blue anthocyanin

Structure of an alkaline hydrolysis product of heavenly blue anthocyanin was determined to be $\text{trans}$-4-0-(6-0-($\text{trans}$-3-0-(β-D-glucopyranosyl)caffeyl)-β-D- glucopyranosyl)caffeic acid ($\text{1}$).     

Synthesis of Two Isomeric Tetrasaccharides 0-α-L-Fucopyranosyl-(1→3) and (1→4)-0-(2-Acetamido-2-Deoxy-β-D-Glucopyranosyl)-(1→3)-0-(β-D-Galactopyranosyl)-(1→4)-D-Glucopyranose and a Related Tetrasaccharide 0-α-L-Fucopyranosyl-(1→3)-0-(2-Acetamido-2-Deoxy-β-D-Glucopyranosyl-(1→6)-0-(β-D-Galactopyranosyl)-(1→4)-D-Glucopyranose

ABSTRACT

Synthesis of three tetrasaccharides, namely, 0-α-L-fucopyranosyl-(1→3)-0-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-(1→3)-0-(β-D-galactopyranosyl)-(1→4)-β-D-glucopyranose (7), 0-α-L-fucopyranosyl-(1→4)-0-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-(1→3)-0-(β-D-galactopyranosyl)-(1→4)-D-glucopyranose (9), and 0-α-L-fucopyransoyl-(1→3)-0-(2-acetamido-2-deoxy-β-D-glucopyransoyl)-(1→6)-0-(β-D-galactopyranosyl)-(1→4)-D-glucopyranose (15) has been described. Their structures have been established by ¹³C NMR spectroscopy.     

Two new 3-oxo-α-ionol glucosides from Urtica laetevirens Maxim

Two new 3-oxo-α-ionol glucoside isomers, (6R,9R)-3-oxo-α-ionol-9-O-β-D-glucopyranosyl (1?→?2)-β-D-glucopyranoside (1) and (6S,9R)-3-oxo-α-ionol-9-O-β-D-glucopyranosyl (1?→?2)-β-D-glucopyranoside (2) were isolated from the aerial parts of Urtica laetevirens Maxim. Their structures, including stereochemistry, were established by spectral analyses (HR-ESI-MS, NMR and CD). Also, 3-oxo-α-ionol glucosides were isolated from Urtica species for the first time.     

黄褐毛忍冬中主皂苷成分的结构解析

报道了黄褐毛忍冬中的两个皂苷主成分, 其中化合物1为新化合物, 并对另一个含量最高的皂苷结构进行了修正.     

Synthesis of the tetrasaccharide repeating unit of the o-specific polysaccharide from salmonella muenster and salmonella minneapolis

The tetrasaccharide β-D-Man-(1→4)-α-L-Rha-(1→3)-D-Gal-(4←1)-α-D-Glc the repeating unit of the O-specific polysaccharide chain of the lipopolysaccharides from Salmonella muenster and S, minneapolis was obtained by glycosylation of benzyl 2,6-di-O-benzyl-4-0(2,3,4-tri-O-benzyl-6-O-benzoyl-α-D-glucopyranosyl)-β-D-galactopyranoside with 3-O-acetyl-4-0-(2,3,4,6-tetra-O-acetyl-β-D-mannopyranosyl)- β-L-rhamnopyranose-1,2-(methylorthoacetate), followed by removal of protecting groups. The structure of the synthetic tetrasaccharide was confirmed by methylation analysis, CrO₃-AcOH oxidation and ¹³C-NMR.     

Glycosides of marine invertebrates. XII. Structure of a new triterpene oligoglycoside from holothurians of familyStichopodidae

From an ethanolic extract of the holothuriansStichopus chloronotus by column chromatography on silica gel a new triterpene oligoside has been isolated the structure of which has been established as 23(S)-acetoxy-3β-{4′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-β-D-glucopyranosyl]-2′-O-[O-(3-O-methyl-β-D-glucopyranosyl(-(1→3)-O-β-D-xylopyranosyl-(1→4)-β-D-glucopyranosyl]-β-D-xylopyranosyloxy}holost-7-ene. A hypothesis has been put forward concerning the biosynthesis of the carbohydrate chains in the glycosides of holothurians of the orderAspidochirota from bioside blocks.     

Struktur der Marsectobiose. Desoxyzucker, 46. Mitteilung

Marsectobiose ( 1 ), a disaccharide isolated from Marsdenia erecta R. Br. , is shown to be 4-O-(3-O-methyl-6-deoxy-β-D-glucopyranosyl)-3-O-methyl-2, 6-dideoxy-D-arabinohexose.     

Constituents of Panacis Japonici Rhizoma. VI The Structure of Chikusetsu-Saponin II,IVC

Chikusetsusaponin II and IVc, the minorsaponins of Panacis japonici rhizoma (rhizome of Panax japonicum C.A. MEYER) have been isolated. The structure of these saponins were established as being oleanolic acid-(3)-[β-D-glucopyranosyl (1→6)]-β-D-glucuronopyranoside and 20S-protopanaxatriol-6-(O-α-L-rhamnopyranosyl (1→2)-β-D-glucopyranoside]-20-O-β-D-glucopyranoside. Chikusetsusaponin II is a new structure, while chikusetsusaponin IVc is identical with ginsenoside-Re, isolated from P. ginseng C. A. MEYER.     

Glycosides of marine invertegrates. XI. Two new triterpene glycosides from holothurians of the familyStichopadidae

By repeated column chromatography on silica gel new glycosides have been isolated from the holothuriansAstichopus multifidus andStichopus chloronotus — astichoposide C and stichoposide C (I and II, respectively). Their structures have been studied with the aid of chemical and physicochemical methods. The complete structures of the glycosides have been established as 23(S)-acetoxy-3β-{4′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-β-D-glucopyranosyl]-2′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-O-β-D-xylopyranosyl-(1→4)-β-D-quinovopyranosyl]-β-D-xylopyranosyloxy}holosta-7,25-diene and -holost-7-ene.     

Biotransformation of ursolic acid by Alternaria longipes AS3.2875

Microbial transformation of ursolic acid (1) was carried out by Alternaria longipes AS 3.2875. Six transformed products (2–7) from 1 were isolated and their structures were identified as 3-carbonyl ursolic acid 28-O-β-D-glucopyranosyl ester (2), ursolic acid 3-O-β-D-glucopyranoside (3), ursolic acid 28-O-β-D-glucopyranosyl ester (4), 2α, 3β-dihydroxy ursolic acid 28-O-β-D-glucopyranosyl ester (5), 3β, 21β dihydroxy ursolic acid 28-O-β-D-glucopyranosyl ester (6), and 3-O-(β-D-glucopyranosyl)- ursolic acid 28-O-(β-D-glucopyranosyl) ester (7) based on the analysis of 1D NMR, 2DNMR and MS data. The product 2 was a new compound among them and showed stronger antibacterial activity against S. aureu, MRSA and MRCA than substrate. In this study, we modified structure of ursolic acid through biotransformation to enhance its activities and preliminarily discussed the transformation way of the products.     

Triterpene glycosides of Hedera taurica X. Structures of compounds F4, I,and J from the leaves of Crimean ivy

Echinocystic acid 3-sulfate and new 3-sulfates — of the 28-O-[O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl esters of oleanolic and echinocystic acids have been isolated from the leaves of Crimean ivyHedera taurica Carr. (fam. Araliaceae).