Four triterpenoid saponins from dried roots of Gypsophila species.

Four new triterpenoid saponins were isolated from the roots of Gypsophila paniculata and G. arrostii. Their structures were elucidated using a combination of homo- and heteronuclear 2D NMR techniques, without having recourse to chemical degradation or modification. The saponins investigated are: 3-O-beta-D-galactopyranosyl-(1----2)-[beta-D-xylopyranosyl-(1----3)]-bet a-D- glucuronopyranosyl quillaic acid 28-O-beta-D-glucopyranosyl-(1----3)-[beta-D-xylopyranosyl-(1----4)]-alph a- L-rhamnopyranosyl-(1----2)-beta-D-fucopyranoside; 3-O-beta-D-galactopyranosyl-(1----2)-[beta-D-xylopyranosyl-(1----3)]-bet a- D-glucuronopyranosyl quillaic acid 28-O-beta-D-arabinopyranosyl-(1----4)-beta-D-arabinopyranosyl++ +-(1----3)-beta-D- xylopyranosyl-(1----4)-alpha-L-rhamnopyranosyl-(1----2)-beta-D-fucopyran oside; 3-O-beta-D-glucopyranosyl-(1----2)-beta-D-glucuronopyranosyl gypsogenin 28-O-beta-D-glucopyranosyl-(1----3)-[beta-D-xylopyranosyl-(1----4)]-alph a- L-rhamnopyranosyl-(1----2)-beta-D-fucopyranoside; 3-O-beta-D-xylopyranosyl-(1----3)-[beta-D-galactopyranosyl-(1----2)]-bet a- D-glucuronopyranosyl gypsogenin 28-O-beta-D-glucopyranosyl-(1----3)-[beta-D-xylopyranosyl-(1----4)-alpha -L- rhamnopyranosyl-(1----2)-beta-D-fucopyranoside.     

Bayogenin and asterogenic acid glycosides from Bellis perennis.

Four novel triterpenoid saponins were isolated from the underground parts of Bellis perennis. The structures were elucidated as 3-O-beta-D-glucopyranosides of 2 beta,3 beta,16 alpha-trihydroxyolean-12-ene-28-oic acid-28-alpha-L- rhamnopyranosyl(1----2)-[beta-D-glucopyranosyl(1----6)]-beta-D- glucopyranoside, 2 beta,3 beta,23-trihydroxyolean-12-ene-28-oic acid-28-O-beta-D-xylopyranosyl (1----2)-[beta-D-glucopyranosyl (1----6)]- beta-D-glucopyranoside and 2 beta,3 beta,23-trihydroxyolean-12-ene-28-oic acid-28-O-alpha-L-rhamnopyranosyl(1----2)-[beta-D-glucopyranosyl(1----6) ]- beta-D-glucopyranoside and as 3-O-alpha-L-rhamnopyranosyl-2 beta,3 beta,23-trihydroxyolean-12-ene-28-oic acid-28-O-beta-D-glucopyranosyl(1----2)-[beta-D-glucopyranosyl(1----6)]- beta-D-glucopyranoside by means of high field 1D and 2D NMR spectroscopic methods without recourse to derivatization or comparison with previous data.     

Triterpene saponins from Cylicodiscus gabunensis.

Four new saponins were isolated from the alcoholic extract of the bark of Cylicodiscus gabunensis by means of flash chromatography. They were characterized on the basis of spectral and chemical data as 3-O-beta-[alpha-L-arabinopyranosyl (1----2),alpha-L-arabinopyranosyl(1----3),beta-D-glucopyranosyl(1- ---)] maslinic acid-28-[beta-D-glucopyranosyl(1----6),beta-D-glucopyranosyl(1----2),alp ha-L- rhamnopyranosyl(1----)] ester; 3-O-beta-[alpha-L-arabinopyranosyl(1----2),alpha-L-arabinopyran osyl (1----3),beta-D-glucopyranosyl(1----)]maslinic acid-28-[beta-D-glucopyranosyl(1----2),alpha-L-rhamnopyranosyl(1----)] ester, 3-O-beta-[alpha-L-arabinopyranosyl(1----2),alpha-L-arabinopyran osyl (1----3),beta-D-glucopyranosyl(1----)]maslinic acid and 3-O-beta(alpha-L-arabinopyranosyl(1----3),beta-D-glucopyranosyl (1----)] cylicodiscic acid.     

Triterpenoidal saponins from Madhuca butyracea.

Two new triterpenoidal saponins, butyrosides A and B, were isolated from the seeds of Madhuca butyracea, along with two known saponins, Mi-saponin A and 16 alpha-hydroxy Mi-saponin A. On the basis of chemical and spectroscopic evidence, the structures of butyrosides A and B were established to be 3-O-beta-D-glucopyranosyl protobassic acid 28-O-beta-D-apiofuranosyl(1----3)-beta-D-xylopyranosyl (----4)-alpha-L-rhamnopyranosyl(1----2)-alpha-L-arabinopyranoside and 3-O-beta-D-glucopyranosyl 16 alpha-hydroxy protobassic acid 28-O-beta-D-apiofuranosyl(1----3)-beta-D-xylopyranosyl (1----4)-alpha-L-rhamnopyranosyl(1----2)-alpha-L-arabinopyranoside , respectively.     

Triterpenoid glycosides from the bark of Mimosa tenuiflora.

Two new saponins were isolated from Mimosa tenuiflora and their structures established as 3-O-[alpha-L-rhamnopyranosyl(1----2)-beta-D-glucopyranosyl-(1----3]-(alp ha-L- arabinopyranosyl-(1----4]-beta-D-xylopyranosyl-(1----2)]-[beta-D- xylopyranosyl-(1----4)]-beta-D-glucopyranosyl)-28-O-alpha-L-rhamnopyrano syl oleanolic acid and 3-O-[alpha-L-rhamnopyranosyl-(1----2)-beta-D-glucopyranosyl-(1----3]-(al pha- L-arabinopyranosyl-(1----4]beta-D-xylopyranosyl-(1----2)]-[beta-D- xylopyranosyl-(1----4)]-beta-D-glucopyranosyl) oleanolic acid.     

Four major saponins from Solidago canadensis.

Four new bisdesmosidic saponins each containing eight carbohydrate units were isolated from Solidago canadensis. GC, GC-MS, FABMS analysis and mainly the use of 2D NMR techniques allowed their identification as bayogeninglycosides (canadensissaponins 1-4) 3-O- [beta-D-glucopyranosyl-(1----3)-beta-D-glucopyranosyl]-28-O-[alpha-L- rhamnopyranosyl-(1----3)-beta-D-xylopyranosyl-(1----4)-[beta-D- xylopyranosyl-(1----3)]-alpha-L-rhamnopyranosyl-(1----2)-[beta-D- apio-D-furanosyl-(1----3)]-beta-D-6-deoxyglucopyranosyl- (1----]-bayogenin; -(1----2)-[beta-D-apio-D-furanosyl-(1----3)]-ara- binopyranosyl-(1----]-bayogenin; -[alpha-L-rhamnopyranosyl-(1----3)]-beta- D-6-deoxyglucopyranosyl-(1----]-bayogenin and - [alpha-L-rhamnopyranosyl- (1----3)]-arabinopyranosyl-(1----]-bayogenin.     

Triterpene saponins from Verbascum songaricum.

Songarosaponin A, B and C isolated from the aerial parts of Verbascum songaricum were shown to be 3-O-[alpha-L-rhamnopyranosyl-(1----4)-beta-D-glucopyranosyl-(1----3)]-[b eta-D-glucopyranosyl-(1----2)-beta-D-fucopyranosyl]-olea-11,13-die ne-3 beta-23,28-triol, 3-0-[alpha-L-rhamnopyranosyl-(1----4)-beta-D-glucopyranosyl-(1----3)]-[b eta-D-glucopyranosyl-(1----2)]-beta-D-fucopyranosyl]-olea-1 1-ene-3 beta-13,23,28-tetrol and 3-O-[beta-D-glucopyranosyl-(1----4)]-[beta-D-glucopyranosyl-(1----3)]-[b eta-D-glucopyranosyl-(1----2)]-beta-D-fucopyranosyl]-13 beta,28-epoxyolea-11-ene-3 beta,23-diol.     

Virgaureasaponin 3, a 3,28-bisdesmosidic triterpenoid saponin from Solidago virgaurea.

A new 3,28-bisdesmosidic triterpenoid glycoside was isolated from the mixture of deacylated saponins from the aerial parts of Solidago virgaurea. The structure of virgaureasaponin 3 was determined as 3-O-beta-D-glucopyranosyl-(1----3)-beta-D-glucopyranosylpolygalacic++ + acid 28-O-beta-D-fucopyranosyl-(1----2)-alpha-L-rhamnopyranosyl-(1----3)-beta -D- xylopyranosyl-(1----4)-alpha-L-rhamnopyranosyl-(1----2)-beta-D-fucopyran oside mainly by various 2D NMR techniques.     

A bidesmosidic triterpenoid saponin from Schefflera octophylla.

A new 3,28-bidesmosidic triterpenoid saponin was isolated from the leaves of Schefflera octophylla together with a new trisaccharide and oleanonic acid. Based on spectroscopic data and chemical transformations, the structures of the new constituents were determined as 3-epi-betulinic acid 3-O-beta-D-glucopyranoside 28-O-[alpha-L-rhamnopyranosyl(1----4)-O-beta-D-glucopyranosyl(1----6)]-b eta- D-glucopyranoside and alpha-L-rhamnopyranosyl(1----4)-O-beta-D-glucopyranosyl(1----6)-beta-D- glucopyranose.     

Saponins from Steganotaenia araliacea.

Six saponins have been isolated and identified from the leaves of Steganotaenia araliacea. They were identified as 3-O-[beta-D-galactopyranosyl(1----2)-(beta-D-galactopyranosyl (1----3))-beta-D-glucuronopyranosyl]-21-O-tigloyl and -21-O-angeloyl-R1-barrigenol, 3-O-[beta-D-glucopyranosyl(1----2)-(beta-D-xylopyranosyl (1----3))-beta-D-glucuronopyranosyl]-21-O-tigloyl and -21-O-angeloyl-R1-barrigenol, 3-O-[beta-D-glucopyranosyl(1----2)-(beta-D-glucopyranosyl-(1----3))-(alp ha-L- rhamnopyranosyl(1----4))-beta-D-glucopyranosyl] steganogenin and 3-O-[(beta-D-galactopyranosyl(1----2)-beta-D-glucuronopyranosyl]-2 8-O- beta-D-glucopyranosyl olean-12-ene-28-oic acid. Steganogenin is a new 17,22-seco-oleanolic acid derivative. The structures of the saponins were established by analysis of their 1H and 13C NMR spectra with the help of 2D-experiments and by Californium Plasma Desorption Mass Spectrometry.     

Structure of the sidechain of lipopolysaccharide from Pseudomonas syringae pv. morsprunorum C28

The sidechain of the lipopolysaccharide from the phytopathogen Pseudomonas syringae pv. morsprunorum C28 was shown to be composed of D-rhamnose. Using 1H and 13C-NMR spectroscopy, methylation analysis, Smith degradation and optical rotation data, the repeat unit was found to have the structure: ----3)-D-Rhap-(alpha 1----3)-D-Rhap-(alpha 1----2)-D-Rhap-(alpha 1---- and a degree of polymerization of approximately 70. Attention is drawn to the possible prevalence of D-6-deoxyhexoses in the lipopolysaccharides of plant pathogenic bacteria.     

A sulphated triterpenoid saponin from Schefflera octophylla.

Dried leaves of Schefflera octophylla afforded a new sulphated triterpene glycoside. From spectroscopic data and chemical transformations the structure of the new constituent was determined as 3-epi-betulinic acid 3-O-sulphate 28-O-[alpha-L-rhamnopyranosyl(1----4)-O-beta-D-glucopyranosyl (1----6)]-beta-D-glucopyranoside.     

A saponin from callus tissue of Stauntonia hexaphylla.

A new 30-nortriterpenoid saponin was isolated from the callus tissues of Stauntonia hexaphylla. The structure of the saponin (tentatively named mubenoside A) was elucidated as 3 beta,20 alpha-dihydroxy-30-nor-olean-12-en-28-oic acid 3-O-[beta-D-xylopyranosyl(1----2)-alpha-L-arabinopyranosyl(1----3) ]-beta-D- glucopyranoside by means of spectral experiments.     

Primary structure of ten galactosides formed by transglycosylation during lactose hydrolysis by Bifidobacterium bifidum

Oligosaccharides formed by a transgalactosylation reaction during lactose hydrolysis with Bifidobacterium bifidum were separated into eight fractions by gel-permeation chromatography and their structures studies determined by trimethylsilylation analysis, methylation analysis, f.a.b.-m.s., g.l.c.-m.s. and enzymic hydrolysis as beta-D-Galp-(1----3)-D-Glc, beta-D-Galp-(1----6)-D-Glc, beta-D-Galp-(1----6)-D-Gal, beta-D-Galp-(1----3)-beta-D-Galp-(1----4)-D-Glc, beta-D-Galp-(1----6)[beta-D-Galp-(1----4)]-D-Glc, beta-D-Galp-(1----2)[beta-D-Galp-(1----6)]-D-Glc, beta-D-Galp-(1----3)-beta-D-Galp-(1----3)-beta-D-Galp-(1----4)-D-Glc, beta-D-Galp-(1----3)-beta-D-Galp-(1----3)-beta-D-Galp-(1----3)-beta-D-Ga lp- (1----4)-D-Glc, beta-D-Galp-(1----3)-beta-D-Galp-(1----3)-beta-DGalp-(1----3)-beta -D-Galp-(1----3)-beta-D-Galp-(1----4)-D-Glc, and beta-D-Galp-(1----3)-beta-D-Galp-(1----3)-beta-D-Galp-(1----3)-beta-D-Ga lp-(1----3)-beta-D-G-alp-(1----3) beta-D-Galp-(1----4)-D-Glc.     

Mouse monoclonal antibodies with specificity for the melanoma-associated ganglioside disialyllactosylceramide (GD3) also react with the structural analogue disialylparagloboside

A mouse monoclonal IgM antibody, 4.2, has previously been shown to bind preferentially to the surface of human malignant melanoma cells and to have specificity for the GD3 ganglioside (NeuAc alpha 2----8NeuAc alpha 2----3Gal beta 1----4GlcCer). Using overlay of antibodies on thin-layer chromatograms with glycolipids of various sources, it was shown that antibody 4.2, a further IgM and two IgG3 mouse monoclonal antibodies, selected on the basis of reactivity with GD3, also bound with similar strength to the structural analogue NeuAc alpha 2----8NeuAc alpha 2----3Gal beta 1----4GlcNac beta 1----3Gal beta 1----4GlcCer or disialylparagloboside. The SK-MEL 28 melanoma cell line used for immunization was shown to contain a large amount of GD3 but to lack disialylparagloboside. The demonstrated cross-reactivity may be of importance when considering the use of these antibodies for biochemical and medical purposes.     

Primary structure of four human milk octa-, nona-, and undeca-saccharides established by 1H- and 13C-nuclear magnetic resonance spectroscopy.

The structures of two octasaccharides, one nonasaccharide, and one undecasaccharide, isolated from human milk, have been investigated by 1H- and 13C-nuclear magnetic resonance spectroscopy. The structures of these oligosaccharides are: beta-D-Galp-(1----4)-[alpha-L-Fucp- (1----3)]-beta-D-GlcpNAc-(1----3)-beta-D-Galp-(1----4)-[alpha-L-Fucp+ ++- (1----3)]-beta-D-GlcpNAc-(1----3)-beta-D-Galp-(1----4)-D-Glc; beta-D-GALp-(1----3)-[alpha-L-Fucp-(1----4)]-beta-D-GlcpNAc-(1---- 3)-beta-D - Galp-(1----4)-[alpha-L-Fucp-(1----3)]-beta-D-GlcpNAc-(1----3)-beta -D-Galp- (1----4)-D-Glc; beta-D-Galp-(1----4)-[alpha-L-Fucp-(1----3)]-beta-D-GlcpNAc-(1---- 6)-(alpha - L-Fucp-(1----2)-beta-D-Gal-(1----3)-[alpha-L-Fucp-(1----4)]- beta-D-GlcpNAc- (1----3))-beta-D-Galp-(1----4)-D-Glc; and alpha-L-Fucp-(1----2)-beta-D-Galp-(1----3)-beta-D-GlcpNAc-(1----3) -beta-D- Galp-(1----4)-[alpha-L-Fucp-(1----3)]-beta-D-GlcpNAc-(1----6)-[alp ha-L- Fucp-(1----2)-beta-D-Galp-(1----3)-beta-D-GlcpNAc-(1----3)]-beta-D -Galp- (1----4)-D-Glc. The two octasaccharides have been previously isolated from human milk as a mixture, and in a pure form from new-born feces, but the n.m.r. data were not provided. These two octasaccharides display the di-Lewis X and the composite Lewis A-Lewis X antigenic determinant, previously described as neo-antigens of adenocarcinoma cell lines.     

The structures of oligosaccharides excreted by sheep with swainsonine toxicosis

Eleven oligosaccharides were purified form the urine of sheep with swainsonine toxicosis induced by the feeding of Astragalus lentiginosus. Oligosaccharides were extracted by charcoal adsorption, chromatographed on Bio-Gel P-2, and partially fractionated by preparative-layer chromatography. Separation into individual compounds was completed by semi-preparative high pressure liquid chromatography. Structures were determined by a combination of high pressure liquid chromatography and exo- and endo- glycosidase action, methanolysis followed by gas-liquid chromatography, methylation analysis, and high resolution nuclear magnetic resonance spectroscopy. Two homologous series of oligosaccharides were identified: (a) alpha-D-Manp-(1----6)-beta-D-Manp-(1----4)-D-GlcpNAc, alpha-D-Manp(1----3)-[alpha-D-Manp-(1----6)]-beta-D-Manp+ ++-(1----4)-D-GlcpNAc, alpha-D-Manp-(1----2)-alpha-D-Manp(1----3)-[alpha-D-Manp+ ++-(1----6)]-beta-D-Manp-(1----4)-D-GlcpNAc, and alpha-D-Manp-(1----2)-alpha-D-Manp-(1----2)-alpha-D-Manp+ ++-(1----3)-[alpha- D-Manp-(1----6)]-beta-D-Manp-(1----4)-D-GlcpNAc (minor series); (b) alpha-D-Manp-(1----6)-beta-D-Manp-(1----4)-beta-D-GlcpNAc- (1----4)-D-GlcpNAc, alpha-D-Manp-(1----3)-[alpha-D-Manp-(1----6)]-beta-D-Manp -(1----4)-beta-D-GlcpNAc-(1----4)-D-GlcpNAc, alpha-D-Manp(1----3)-alpha-D-Manp-(1----6)-beta-D-Manp -(1----4)-beta-D-GlcpNAc- (1----4)-D-GlcpNAc, alpha-D-Manp-(1----6)-alpha-D-Manp-(1----6)-beta-D-Manp++ +-(1----4)-beta-D-GlcpNAc - (1----4)-D-GlcpNAc, alpha-D-Manp-(1----3)-alpha-D-Manp-(1----6)-[alpha-D-Manp -(1----3)]-beta-D- Manp-(1----4)-beta-D-GlcpNAc-(1----4)-D-GlcpNAc, alpha-D-Manp-(1----3)-[alpha-D-Manp-(1----6)]-alpha-D-Man p-(1----6)-beta-D- Manp-(1----4)-beta-D-GlcpNAc-(1----4)-D-GlcpNAc, and alpha-D-Manp-(1----3)-[alpha-D-Manp-(1----6)]-alpha-D-Man p-(1----6)- [alpha-D-Manp-(1----3)]-beta-D-Manp-(1----4)-beta-D-GlcpNAc- (1----4)-D- GlcpNAc (major series).     

The c-series gangliosides GT3, GT2 and GP1c are formed in rat liver Golgi by the same set of glycosyltransferases that catalyse the biosynthesis of asialo-, a- and b-series gangliosides.

Biosynthesis of the c-series gangliosides GT3, GT2 and GP1c was studied in Golgi derived from rat liver. Competition experiments show that the synthesis of ganglioside GT2 (GalNAc beta 1----4-(NeuAc alpha 2----8NeuAc alpha 2----8NeuAc alpha 2----3)Gal- beta 1----4Glc beta 1----1Cer) from GT3 (NeuAc alpha 2----8NeuAc alpha 2----8-NeuAc alpha 2----3Gal beta 1----4Glc beta 1----1Cer) seems to be catalysed by the same N-acetylgalactosaminyl-transferase (GalNAc-T), which converts GM3 (NeuAc alpha 2----3Gal beta 1----4Glc beta 1----1Cer) to GM2 (GalNAc beta 1----4(NeuAc alpha 2----3)Gal beta 1----4Glc beta 1----1Cer). Similar competition experiments suggest moreover that the sialytransferase V (SAT V), which catalyses the synthesis of GT1a (NeuAc alpha 2----8NeuAc alpha 2----3Gal beta 1----3GalNAc beta 1----4- (NeuAc alpha 2----3)-Gal beta 1----4Glc beta 1----1Cer) from GD1a (NeuAc alpha-2----3Gal beta 1----3GalNAc beta 1----4(NeuAc alpha 2----3)Gal beta 1----4Glc beta 1----1-Cer) appears to be identical to the enzyme that catalyses the synthesis of GP1c (NeuAc alpha 2----8NeuAc alpha 2----3Gal beta 1----3-GalNAc beta 1----4(NeuAc alpha 2----8-NeuAc alpha 2----8NeuAc alpha 2----3)Gal beta-1----4Glc beta 1----4Glc beta 1----1Cer) from GQ1c (NeuAc alpha 2----3Gal beta 1----3Gal-NAc beta 1----4 (NeuAc alpha 2----8NeuAc alpha 2----8NeuAc alpha 2----3)Gal beta 1----4-Glc beta 1----1Cer).(ABSTRACT TRUNCATED AT 250 WORDS)     

Primary structure determination of five sialylated oligosaccharides derived from bronchial mucus glycoproteins of patients suffering from cystic fibrosis. The occurrence of the NeuAc alpha(2----3)Gal beta(1----4)[Fuc alpha(1----3)] GlcNAc beta(1----.) structural element revealed by 500-MHz 1H NMR spectroscopy

The structure of sialylated carbohydrate units of bronchial mucins obtained from cystic fibrosis patients was investigated by 500-MHz 1H NMR spectroscopy in conjunction with sugar analysis. After subjecting the mucins to alkaline borohydride degradation, sialylated oligosaccharide-alditols were isolated by anion-exchange chromatography and fractionated by high performance liquid chromatography. Five compounds could be obtained in a rather pure state; their structures were established as the following: A-1, NeuAc alpha(2----3)Gal beta(1----4) [Fuc alpha(1----3)]GlcNAc beta(1----3)Gal-NAc-ol; A-2, NeuAc alpha(2----3)Gal beta(1----4)GlcNAc beta(1----6)-[GlcNAc beta (1----3)]GalNAc-o1; A-3, NeuAc alpha(2----3)Gal beta-(1----4)[Fuc alpha(1----3)]GlcNAc beta(1----3)Gal beta(1----3) GalNAc-o1; A-4, NeuAc alpha(2----3)Gal beta(1----4)[Fuc alpha(1----3)]Glc-NAc NAc beta(1----6)[GlcNAc beta(1----3)]GalNAc-o1; A-6,NeuAc alpha-(2----3) Gal beta(1----4)[Fuc alpha(1----3)]GlcNAc beta(1----6)[Gal beta-(1----4) GlcNAc beta(1----3)]GalNAc-o1. The simultaneous presence of sialic acid in alpha(2----3)-linkage to Gal and fucose in alpha(1----3)-linkage to GlcNAc of the same N-acetyllactosamine unit could be adequately proved by high resolution 1H NMR spectroscopy. This sequence constitutes a novel structural element for mucins.     

Synthesis of trisaccharide methyl glycosides related to fragments of the capsular polysaccharide of Streptococcus pneumoniae type 18C.

The synthesis is reported of methyl 3-O-(4-O-beta-D-galactopyranosyl-alpha-D- glucopyranosyl)-alpha-L-rhamnopyranoside (1), methyl 2-O-alpha-D-glucopyranosyl-4-O-beta-D-glucopyranosyl-beta-D- galactopyranoside (3), methyl 3-O-(4-O-beta-D-galactopyranosyl-alpha-D-glucopyranosyl)-alpha-L- rhamnopyranoside 3"-(sn-glycer-3-yl sodium phosphate) (2), and methyl 2-O-alpha-D-glucopyranosyl-4-O-beta-D- glucopyranosyl-beta-D-galactopyranoside 3-(sn-glycer-3-yl sodium phosphate) (4), which are trisaccharide methyl glycosides related to fragments of the capsular polysaccharide of Streptococcus pneumoniae type 18C ([----4)-beta-D- Glcp-(1----4)-[alpha-D-Glcp-(1----2)]-[Glycerol-(1-P----3)]-beta-D-Galp - (1----4)-alpha-D-Glcp-(1----3)-alpha-L-Rhap-(1----]n). Ethyl 4-O-acetyl-2,3,6-tri-O-benzyl-1-thio-beta-D-glucopyranoside (10) was coupled with benzyl 2,4-di-O-benzyl-alpha-L-rhamnopyranoside (6). Deacetylation of the product, followed by condensation with 2,4,6-tri-O-acetyl-3-O-allyl-alpha-D-galactopyranosyl trichloroacetimidate (18), gave benzyl 2,4-di-O-benzyl-3-O-[2,3,6-tri-O- benzyl-4-O-(2,4,6-tri-O-acetyl-3-O-allyl-beta-D-galactopyranosyl)-alpha- D- glucopyranosyl]-alpha-L-rhamnopyranoside (19). Acetolysis of 19, followed by methylation, deallylation (----22), and further deprotection afforded 1. Condensation of methyl 2,4-di-O-benzyl-3-O-[2,3,6-tri-O-benzyl-4-O-(2,4,6-tri- O-acetyl-beta-D-galactopyranosyl)-alpha-D-glucopyranosyl]-alpha-L- rhamnopyranoside (22) with 1,2-di-O-benzyl-sn-glycerol 3-(triethyl-ammonium phosphonate) (24), followed by oxidation and deprotection, yielded 2. Condensation of ethyl 2,3,4,6-tetra-O-benzyl-1-thio-beta-D-glucopyranoside (27) with methyl 3-O-allyl-4,6-O-benzylidene-beta-D-galactopyranoside (28), selective benzylidene ring-opening of the product, coupling with 2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl trichloroacetimidate (31), and deallylation afforded methyl 6-O-benzyl-4-O-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-2-O- (2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl)-beta-D-galactopyranoside (33). Deprotection of 33 gave 3, and condensation of 33 with 24, followed by oxidation and deprotection, gave 4.