ChemInform Abstract: A NOVEL SYNTHESIS OF 1,2‐CIS‐DISACCHARIDES

Pougny, Jean Rene; Jacquinet, Jean Claude; Nassr, M. A. M.; Duchet, D.; Milat, M.-L.; Sînaÿ, Pierre

doi:10.1002/chin.197801363

Cited by 2 publications

(4 citation statements)

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“…Protected Trehalose 7 4,6,4',2',3, (1.0 g)13) in methanol -chloroform 4,6-O-benzylidene-2,2',3,3'-tetra-O-benzoyl-D-trehalose (0.2 g) in dry pyridine (2 ml) was treated at 0°C with benzoyl chloride (1.0 molar equiv.) overnight.…”

Section: Methodsmentioning

confidence: 99%

New .ALPHA.-amylase inhibitor, trestatins. II. structure determination of trestatins A, B and C.

Yokose¹,

Ogawa²,

Suzuki³

et al. 1983

J. Antibiot.

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The structures of trestatins A (C56H94N2O40), B (C37H63NO23) and C (C75H125N3O52), new basic oligosaccharides with potent inhibitory activity against various a-amylases, have been shown by spectroscopic and chemical methods to be 1, 2 and 3, respectively.Trestatin complex (Ro 09-0154) which is produced by a novel streptomycete, Streptomyces dimorphogenes NR320-OM7HB, contains new potent a-amylase inhibitors. We reported in the previous paper1) the isolation and characterization of three major components of trestatin complex, trestatins A, B and C, all of which are water-soluble basic oligosaccharides consisting of D-glucose and the pseudodisaccharide, dehydro-oligobiosamine6) 4 (Fig. 1).In the present paper, we describe the structural elucidation of the molecular structures of the homologous oligosaccharides, trestatins A, B and C. Results and Discussion Structures of Glucotriose and GlucotetraoseIn order to determine the sequences, each trestatin (A, B and C) was subjected to mild acid hydrolysis using Dowex 50 (H+ form) as described in the previous paper1), and partially hydrolyzed products were separated into neutral and basic fragments. HPLC analysis of the neutral fragments from each trestatin showed identical chromatograms which revealed the presence of glucose, maltose, a,a-trehalose, glucotriose (5a) and glucotetraose (6a). Acetylation of the neutral fragments with acetic anhydride in pyridine followed by chromatography on silica gel gave peracetates of D-glucose, D-maltose, a,a-Dtrehalose, glucotriose (5a) and glucotetraose (6a). Each peracetate of the glucotriose and the glucotetraose obtained from trestatins A, B and C showed identical physico-chemical properties indicating that trestatins A, B and C contained the same partial structure. The glucotriose peracetate (5b) showed the highest peak at m/z 906 (M-AcOH)+ in the EI-MS. 0 I The 114 NMR spectrum of 5b in CDCl3 showed no signal assignable to -CH-OAc at 8 5.6~6.5, indicating that 5b contained a,a-trehalose moiety. The 13C NMR spectrum of 5b showed anomeric carbons at d 95.7 and 91.8 (x2) assignable to a-(1-->4) and a,a-(l4-->1) linkages, respectively2). This spectral evidence indicated that the triose 5a was 4-O-a-D-glucopyranosyl-a,a-trehalose, which was confirmed by the chemical synthesis of perbenzoate 5c starting from a,a-trehalose and methyl-a-D-glucoside as shown in Scheme 13).The glucotetraose peracetate (6b) showed a molecular ion peak at m/z 1,255 (MH+ for glucotetraose peracetate, CS52H70O35) in its FD-MS. The 1H NMR spectrum of 6b was similar to that of 5b, also indi-O I cating the absence of -CH-OAc.The 13C NMR spectrum of 6b in CDCl3 showed at least 22 carbon signals attributable to sugar skeleton, of which four anomeric carbons were observed at 8 95.6 (x 2) and 91.8 (x2) assignable to a-(1-->4) and a,a-(1E->1) linkages, respectively. From these results, the tetraose 6a was indicated to be 4-O-a-maltosyl-a,a-trehalose.These assignments were supported by GC-MS analysis of methylated alditol acetates obtained from each trestatin accordi...

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Section: Methodsmentioning

confidence: 99%

New .ALPHA.-amylase inhibitor, trestatins. II. structure determination of trestatins A, B and C.

Yokose¹,

Ogawa²,

Suzuki³

et al. 1983

J. Antibiot.

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“…2,3,4-Tri-O-benzyl-a-~-fucopyranose (1) was conveniently and quantitatively transformed into crystalline 2,3,4-t ri-0-benzyl-a-~-f ucopyranos yl chloride (2) under the agency of dimethylchloroformadinium R' Condensation of the imidate (3) with benzyl2-acetamido-3-0-allyl-6-0-benzyl-2-deoxy-a-~-glucopyranoside (4) in nitromethane in the presence of anhydrous toluene-$sulphonic acid and powdered molecular sieves (4 A) (16 h at room temperature) gave the protected disaccharide (6) in high yield (93%). The disaccharide (6) was 0-deallylated with chloro[tris(triphenylphosphine)]rhodium(1) l1 in benzene-ethanol-water at reflux temperature during 5 days to obtain the alcohol (7), which did not crystallise but was transformed into its crystalline acetate (8). The structure of the disaccharide (7) was ascertained after hydrogenolysis to the known disaccharide (9) .8b Owing to its high degree of crystallinity, its stability on storage, and its ease of preparation, the imidate (3) is a useful a-L-fucosylating agent and use of the sensitive 2 , 3,4-t ri-0-benzyl-a-~-f ucopyranosyl bromide is avoided.…”

Section: Lemieux and D R I G U E Z ~mentioning

confidence: 99%

“…The disaccharide (7) (100 mg) was acetylated for 72 h with acetic anhydride (0.5 ml) in dichloromethane (10 ml) containing pyridine (0.5 ml). After usual work-up, the product was crystallised from ether-hexane to give the disaccharide (8) (96 mg, 91yo), m.p. 80-82" (with evolution of a gas a t 45" and softening a t 60-61°), [a], +2" (c 1 in chloroform), 6 1.05 (3 H, d, 7 Hz, Me), 1.86 and 2.00 (6 H, Hz, H-l'), 5.70 (1 H, d, J 9 Hz, NH), and 7.30 and 7.32 (25 H, Ph) (Found: C, 70.75; H, 6.6; N, 1.55; 0, 20.55.…”

Section: Benzyl2-a Cetamido-3-o-acetyl-6-o-benzyl-4-0-( 234-tri-obenz...mentioning

confidence: 99%

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Synthesis of blood-group substances. Part 8. A synthesis of the branched trisaccharide 2-acetamido-2-deoxy-4-O-(α-L-fucopyranosyl)-3-O-(β-D-galactopyranosyl)-D-glucopyranose

Jacquinet¹,

Sînaÿ²

1979

J. Chem. Soc., Perkin Trans. 1

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ChemInform Abstract: A NOVEL SYNTHESIS OF 1,2‐CIS‐DISACCHARIDES

Abstract: Über das β‐D‐Glucopyranosederivat (II) können die Disaccharide (IIIa) und ‐ auf analoge Weise ‐ (IIIb) dargestellt werden (stereospezifische α‐D‐Glucosylierung).

Cited by 2 publications

References 1 publication

New .ALPHA.-amylase inhibitor, trestatins. II. structure determination of trestatins A, B and C.

New .ALPHA.-amylase inhibitor, trestatins. II. structure determination of trestatins A, B and C.

Synthesis of blood-group substances. Part 8. A synthesis of the branched trisaccharide 2-acetamido-2-deoxy-4-O-(α-L-fucopyranosyl)-3-O-(β-D-galactopyranosyl)-D-glucopyranose

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