Action of Strong Acids on Acetylated Glycosides. V. Synthesis of beta-Isomaltose Octaacetate.

Lindberg, Bengt; Hirsjärvi, Pekka; Melaja, Asko; Kainulainen, Aune; Halonen, Aira; Pulkkinen, Erkki

doi:10.3891/acta.chem.scand.03-1355

Cited by 33 publications

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“…The first preparation of an a-D-glucopyranosyl disaccharide was by ano~rlerization of gentiobiose t o isomaltose by Lindberg in 1949 (8). Goldstein and Whelan (9) applied this method to convert synthetic 6 -~-(~-~-g l~l c 0 p y r a~0 s y 1 ) -~-g a l a c t 0~e to the r-anomer, compound 1 of the present research.…”

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confidence: 99%

Chemical Syntheses of α-Linked Disaccharides

Lemieux¹,

James²,

Nagabhushan³

1973

Can. J. Chem.

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Chemical syntheses of six a-linked disaccharides are described, namely, 6-0-(a- [Traduit par le journal]DCan J Cheili 51 J? (1973) This paper presents syntheses of the six a-linked disaccharides (I to 6) from previously reported (1) oximino-disaccharide structures; namely, the tri-0-acetyl-2-oxin7ino-a-D-arabiko-hexopyranosyl and tri-0-acetyl-2-oxirnino-a-D-/jlxo-hexopyranosyl derivatives of 1,2;5,6-di-0-isopropyiidene-a-D-glucofuranose and of 1,2;3,4-di-0-isopropylidene-a-D-galaclopyranose. The latter compounds were deoximated (2) and the resulting ketonic substances were reduced with sodium borohydride (3) without prior purification. In the preparation of compounds 4, 5, and 6, the use of acetaldehyde in acetonitrilehydrochloric acid reagent (2) for deoximation caused substantial loss of the acid labile 5,6-0-isopropylidene protecting group. However, in the preparation of compounds 1, 2, and 3, deoxirnation under similar conditions caused only small losses of the 0-In view of the high degree of stereoselectivity observed in the reductions to a-D-glucopyranosides (3), the preparations of compounds B and 4 proceeded with little difficulty in 54 and 67% yields, respectively. Although both the interme-propylidene-a-u-galactopyranose and its tetraacetate failed to crystallize, both 3-0-(a-D-glucopyranosyl) -1,2 i5.6-di-0-isopropylidene-a-D-glucofuranose and its tetraacetate were obtained in crystalline condition.As previously reported (3), the reduction of a tri-0-acetyl-a-D-lyxo-hexosuloside with sodium borohydride leads to a mixture of galactosides and talosides. 6-0-(Tetra-0-acetyl-x-D-galactopyranosyl) -1,2:3,4-di-0-isopropylidene-a -D-galactopyranose was obtained crystalline in 51%yield and was readily separated from 6-0-(tetraisopropylidene groups. Treatment of the crude 0-acetyl-a-D-talopyranosy1)-1 ,2:3,4-di-0-isoproketones in these cases with 2,2-dirnethoxypropane pylidene-a-D-galactopyranose (30$/: yield as a andp-to!uenesulfonic acid monohydrate re-intro-syrup) by column chromatography on silicic acid. duced these groups in near quantitative yields. This was not the case in the preparation of compounds 4, 5, and 6. Therefore, lor the syl~tllesis of these compounds deoximation under neutral conditions with titanium trichloride (3, 4) was used. Reduction followed by 0-acetylation enabled compounds 1 to 4 to be isolated as the O-(tetra-8-acetyl-31-~-P1exopyranosy~)-di-0-isopropylidene-D-hexoses. 'Presented at the ihlst National American Chemical Society Meeting, Eos Angeles, California, March 28,1971. 'University of Alberta Postdoctoral Fellow, 1970. 3Professional Research Associate, 1970 Column chromatography on a resin in the hydroxide fornu (5) was used to separate 3-0-(a-Dgalactopyranosyl) -1,2:5,6-di -0 -isopropylidener-D-glucofuranose from the talo-isomer. Both compou~lds were obtained crystalline. The disaccharides (I to 6) were prepared from the di-0-isopropylider?e derivatives by hydrolysis of the isopropylidene groups using aqueous triAuoroacetic acid (6) followed by chromatographic purificat...

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confidence: 99%

Chemical Syntheses of α-Linked Disaccharides

Lemieux¹,

James²,

Nagabhushan³

1973

Can. J. Chem.

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“…Titanium tetrachloride was the more effective catalyst and the method has found wide application for the preparation of alkyl glycosicles anomeric to the form obtained by the I<oenigs-I<norr reaction with stable 1,2-cis-0-acetylglycosyl halides (11,14,21,22,24). In 1944, Lindberg (10) showed that the 0-acetylated ethyl P-glycopyranosides of D-glucose and cellobiose are rearranged to the a-anomer by heating a solution in benzene with hydrogen bromide and mercuric bromide.…”

Section: Introductionmentioning

confidence: 99%

“…When the experiment was interrupted a t the rotation peak of -114", a 14% yield of methyl P-D-arabinopyranoside triacetate was obtained. In more recent years, Lindberg has studied the polarimetric rates for the reactions of a variety of P-D-glucosides (12,13,14), P-D-galactnsides (I), and p-D-xylosides (2) in 10 : 3 mixtures of acetic anhydride -acetic acid with sulphuric acid a s catalyst. In most cases there was a rapid increase in rotation followed by a decrease to a constant value.…”

Section: Introductionmentioning

confidence: 99%

A Mechanism for the Anomerization of Acetylated Alkyl Glycopyranosides

Lemieux¹,

Shyluk²

1955

Can. J. Chem.

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Unequivocal evidence that the anomerizztion of acetylated alkyl glycopyranosides can proceed by way of a n intramolecular mechanism was obtained .I hrough the observation that a racemic misture of methyl 0-glucopyranoside tetraacetete with the D-isomer labelled in the methosyl group with carbon-14 is anomerized both by titanium tetrachloride and boron trifluoride without transfer of radioactive methoxyl groups to the L-isomer. I t is submitted that these intramolecular anomerizations are best rationalized as the result of an unsuccessful attempt by the environment to bring about glycosidic cleavage and proceed b y way of 211 ion-pair intermediate in which the anion is derived from the aglycon group.

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Ergebnisse und Probleme der O‐Glykosidsynthese

Wulff¹,

Röhle²

1974

Angewandte Chemie

134

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Die Synthese von biologisch wichtigen Naturstoffen mit mehr oder minder kompliziertem Kohlenhydratanteil wirft erhebliche Probleme auf. Im vorliegenden Fortschrittsbericht wird über neuere Entwicklungen bei der Knüpfung der O‐Glykosidbindung — ausgehend von 1‐Halogenzuckern und von 1,2‐Zuckerorthoestern — berichtet. Dabei wird versucht, aufgrund reaktions‐mechanistischer Überlegungen vor allem den stereochemischen Ablauf von Glykosylierungsreaktionen besser zu verstehen. Die Untersuchung der Silbersalzabhängigkeit der Koenigs‐Knorr‐Synthese führte zu präparativen Verbesserungen des Verfahrens und zu neuen Vorstellungen über den Reaktionsablauf. Eine wesentliche Bereicherung der präparativen Möglichkeiten zur Synthese von trans‐Glykosiden war die Einführung von 1,2‐Zuckerorthoestern als Glykosylierungskomponente. Sehr bemerkenswerte Fortschritte sind vor allem auch bei der Synthese von cis‐Glykosiden, u. a. durch Ausnutzung von neuartigen Nachbargruppeneffekten, zu verzeichnen.

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Action of Strong Acids on Acetylated Glycosides. V. Synthesis of beta-Isomaltose Octaacetate.

Cited by 33 publications

References 0 publications

Chemical Syntheses of α-Linked Disaccharides

Chemical Syntheses of α-Linked Disaccharides

A Mechanism for the Anomerization of Acetylated Alkyl Glycopyranosides

Ergebnisse und Probleme der O‐Glykosidsynthese

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