Alcohols of the Sugar Group. IV. 2,5-Anhydro-L-iditol

Vargha, L.; Puskás, T.; Nagy, Emma E.

doi:10.1021/ja01181a080

Cited by 10 publications

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“…published a series of papers (4-7) dealing with the structure and reactivity of different furyl-2-ketoxime derivatives, including 2-acetylbenzofuran, but n o new structure was suggested for the acetal 111. Later Greene and Lewis (8) investigating the acid-catalysed rearrangement of 2-acetylfuran oxime tosylate (VI), could show that the diacetal formed possesses, instead of strut.ture VII proposed earlier (9), the cyclic structure VI11.…”

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confidence: 97%

Reinvestigation of the rearrangement of 2‐acetylbenzofuran oxime tosylate

Vargha¹,

Kuszmann²,

Sohár³

et al. 1972

Journal of Heterocyclic Chem

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The acetal, resulting from the rearrangement of anti-2-acetylbenzofuran oxime tosylate (1) was proved to be a mixture of trans-( 1 9 and cis-(X) 2,3-dihydro-2-acetyI-2,3-dimethoxybenzofuran. The structure of these isomers as well as that of their oximes XI and XI1 was elucidated by ir, nmr, and mass spectral investigation and by the ir and nmr spectra of the benzoyl (XI11 and XlV) and acetyl (XV and XVI) derivatives of the oximes. A new reaction mechanism concerning the rearrangement process is discussed.

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confidence: 97%

Reinvestigation of the rearrangement of 2‐acetylbenzofuran oxime tosylate

Vargha¹,

Kuszmann²,

Sohár³

et al. 1972

Journal of Heterocyclic Chem

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“…Our crystallographica nalysisp rovides general insight into the structure-function relationshipso fd iol recognition by boronate groups. Even thought he sugar/diol-binding activity of boric acid andits derivatives has been knownfor almost ac entury, [11] structural information on corresponding complexes has remained scarce and was mainly based on conductivity and/or spectroscopic [12] as well as NMR measurements. [13] So far,only a few X-ray structures have been elucidated for cyclic diesters between boronic acids and diol compounds:1 )a small-molecule complex between m-aminophenylboronatea nd catechol [aqua-2-(3-aminophenyl)benzo-1,3,2-dioxaborole] [9] and 2) complexes between enzymes andb oronic acid inhibitors conjugated to glycerol.…”

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A Tetrahedral Boronic Acid Diester Formed by an Unnatural Amino Acid in the Ligand Pocket of an Engineered Lipocalin

2019

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Boronic acids have long been known to form cyclic diesters with cis‐diol compounds, including many carbohydrates. This phenomenon was previously exploited to create an artificial lectin by incorporating p‐borono‐l‐phenylalanine (Bpa) into the ligand pocket of an engineered lipocalin, resulting in a so‐called Borocalin. Here we describe the X‐ray analysis of its covalent complex with 4‐nitrocatechol as a high‐affinity model ligand. As expected, the crystal structure reveals the formation of a cyclic diester between the biosynthetic boronate side chain and the two ortho‐hydroxy substituents of the benzene ring. Interestingly, the boron also has a hydroxide ion associated, despite an only moderately basic pH 8.5 in the crystallization buffer. The complex is stabilized by a polar contact to the side chain of Asn134 within the ligand pocket, thus validating the functional design of the Borocalin as an artificial sugar‐binding protein. Our structural analysis demonstrates how a boronate can form a thermodynamically stable diester with a vicinal diol in a tetrahedral configuration in aqueous solution near physiological pH. Moreover, our data provide a basis for the further engineering of the Borocalin with the goal of specific recognition of biologically relevant glycans.

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Untersuchungen über Diepoxyhexite. Bildung von 1.6‐Anhydro‐hexiten

Vargha¹,

Kasztreiner²

1960

Chem. Ber.

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1.3.S.6-Tetraacetyl-2.4-athylid1?n-D-sorbit (XIX)a) 0.4 g (0.002 Mol) 2.4-Athyliden-D-glucuron werden reduziert, wie fiir die Darstellung des 2.4-Benzyliden-~-sorbits beschrieben. Die rnit verd. Essigsaure angesauerte Losung wird i. Vak. eingedampft, das zuriickbleibende 61 in Chloroform aufgenommen, die Losung mit Natriumsulfat getrocknet und i. Vak. eingedampft. Den dabei entstandenen, siruposen 2.4-Athyliden-D-sorbit acetyliert man 16 Stdn. mit 10 ccm Pyridin und 4 ccm Acetanhydrid bei 20", gieRt in 50 ccm Eiswasser, extrahiert funfmal mit je 10 ccm Chloroform, wlscht die vereinigten Extrakte rnit Losungen von Kaliumhydrogensulfat und Natriumhydrogencarbonat sowie mit Wasser, trocknet iiber Natriumsulfat, dampft i. Vak. ein und kristallisiert den Riickstand aus 70-proz. Athano1 um. Ausb. 0.12 g (16% d. Th.), Nadeln, Schmp. 116 bis 117'. Lit.6): 117--118". b) 2.3 g (0.01 Mol) I .3;2.4-DiiithyIiden-~-sorbit6) werden rnit 20 ccm 50-proz. Essigsaure 150 Min. in einem Wasserbad auf 95" erwarmt. Dann dampft man i. Vak. bei 35" Badtemp. zu einem Sirup ein, nimmt diesen in Chloroform auf, trocknet die Lasung mit Natriumsulfat, dampft ein und acetyliert den zuriickbleibenden Sirup und arbeitet auf, wie unter a) angegeben. Ausb. 0.56 g (15% d. Th.), Schmp. 115---117". Herrn Professor D r . F. M i c h e e l zi4m 60. GeburtstagBei der alkalischen Hydrolyse des 1.2;5.6-Dianhydro-3.4-isopropyliden-~mannits (I), a-sorbits (11) und -L-idits (Ill) bilden sich neben den entsprechenden 3.4-Isopropyliden-hexiten, wie wir annehmen ohne Konfigurationsinderung, auch 1.6-Anhydro-3.4-isopropyliden-hexite (VII, V111, IX), welche nach Entfernung der Isopropyliden-Gruppe kristallisierte 1.6-Anhydro-hexite liefern (X, XI, XU). Die bei der Bildung von VII, VIII und IX beobachteten sehr unterschiedlichen Ausbeuten lassen sich durch stereochemische Faktoren erklaren.Die Hydrolyse der Diepdxyde I, I1 und Ill mit verd. Schwefelsiiure fiihrt auDer zu Hexiten ebenfalls zu Anhydrohexiten, welche aber rnit X, XI und XI1 nicht identisch sind. Das D-Sorbit-Derivat 11 liefert 2.5-Anhydro-~-idit.Bekanntlich verlauft die hydrolytische affnung der 1.2-Epoxyd-Ringe von Polyhydroxy-Verbindungen nicht immer einheitlich, oft bilden sich infolge einer Ringumlagerung neben den envarteten a-Diolen auch Anhydro-Derivate. So hat L. VARGHA *) Anschrift: Budapest VII., Rottenbiller u. 26.

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Alcohols of the Sugar Group. IV. 2,5-Anhydro-L-iditol

Cited by 10 publications

References 0 publications

Reinvestigation of the rearrangement of 2‐acetylbenzofuran oxime tosylate

Reinvestigation of the rearrangement of 2‐acetylbenzofuran oxime tosylate

A Tetrahedral Boronic Acid Diester Formed by an Unnatural Amino Acid in the Ligand Pocket of an Engineered Lipocalin

Untersuchungen über Diepoxyhexite. Bildung von 1.6‐Anhydro‐hexiten

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