Zur Synthese. von D‐Glucopyrano‐(cis‐2′, 1′‐c)‐l,2,3,4‐tetrahydro‐isochinolinen

Wacker, O.; Fritz, Helmut

doi:10.1002/hlca.19670500833

Cited by 8 publications

(9 citation statements)

References 8 publications

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“…The l-(9-fluorenyl)-1-deoxyglucose (mp 86-88 °C) was prepared similarly from lithiofluorene and 2,3,4,6-tetrabenzylgluconolactone. The 7V-benzyl-2-amino-2-deoxyglucose derivatives were prepared by reductive animation of 2amino-2-deoxyglucose as described by Wacker (1967). The 3-glucosidase, from sweet almonds, was obtained from Sigma Chemical Co. (type I, specific activity usually ~24 units/mg).…”

Section: Methodsmentioning

confidence: 99%

Reversible inhibitors of .beta.-glucosidase

Dale¹,

Ensley²,

Kern³

et al. 1985

Biochemistry

202

120

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A variety of reversible inhibitors of sweet almond beta-glucosidase were examined. These included simple sugars and sugar derivatives, amines and phenols. With respect to the sugar inhibitors and, indeed, the various glycoside substrates, the enzyme has what can be considered a "relaxed specificity". No single substituent on glucose, for example, is essential for binding. Replacement of a hydroxyl group with an anionic substituent reduces the affinity while substitution with a cationic (amine) substituent enhances the affinity. Amines, in general, are good inhibitors, binding more tightly than the corresponding alcohols: pKiRNH3+ = 0.645pKiROH + 1.77 (n = 9, r = 0.97). The affinity of a series of 10 primary amines was found to be strongly influenced by substituent hydrophobicity: pKi = 0.52 pi + 1.32 (r = 0.95). The major binding determinant of the glycoside substrates is the aglycon moiety. Thus, the Ki values of phenols are similar in magnitude to the Ks values of the corresponding aryl beta-glucoside. The pH dependence for the inhibition by various phenols indicates that it is the un-ionized phenol which binds to the enzyme when an enzymic group of pKa = 6.8 (+/- 0.1) is protonated. The affinity of the phenol inhibitor is dependent on its basicity with a Brønsted coefficient for binding of beta = -0.26 (n = 14, r = 0.98). The pH dependence of the binding of two particularly potent beta-glucosidase inhibitors was also examined. 1-Deoxynojirimycin (1,5-dideoxy-1,5-imino-D-glucitol) has a pH-corrected Ki = 6.5 microM, and D-glucono-1,5-lactam has a pH-corrected Ki = 29 microM.(ABSTRACT TRUNCATED AT 250 WORDS)

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Section: Methodsmentioning

confidence: 99%

Reversible inhibitors of .beta.-glucosidase

Dale¹,

Ensley²,

Kern³

et al. 1985

Biochemistry

202

120

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“…Finally, anomerically unprotected imines, susceptible of the intramolecular bonding, will also enable their equilibration in different solvent systems. 18, 20b 19, 20a 21, and 22 9 have been described previously, while compounds 14, 17, 20, and 23−30 are reported herein for the first time. In general, the resulting Schiff bases are usually pure and can be used without further purification.…”

Section: ■ Introductionmentioning

confidence: 60%

“…The glucopyranose structure of 11−30 can further be confirmed by transforming some unprotected compounds into the corresponding per-Oacetyl derivatives (such as 43 and 44), which were obtained in good yields, by treatment with acetic anhydride in pyridine at ambient temperature. 6,9 The formation of α-anomers (like 46 and 47), however, requires an indirect approach starting from 1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-α-D-glucopyranose hydrobromide (45). 4b,24 In order to disentangle the behavior of the anomeric carbon from the rest of the molecule, the synthesis of acylated imines leaving unprotected the anomeric hydroxyl was undertaken too.…”

Section: ■ Introductionmentioning

confidence: 99%

“…This configurational pattern should reasonably be ascribed to the anomeric effect that would favor the axial disposition of the hydroxyl group. As strange as it may be, the literature points to the prevalent β configuration (equatorial anomeric hydroxyl) for the imines derived from 1 and 3 and aromatic aldehydes ( 7 – 10 ). − However, the opposite α-configuration for imines derived from 1 and their acetyl derivatives was postulated in previous work . From a synthetic viewpoint, such imines have been advantageously used not only to protect the amino group but also to switch the anomeric configuration of 2-amino-2-deoxyaldoses.…”

Section: Introductionmentioning

confidence: 99%

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A True Reverse Anomeric Effect Does Exist After All: A Hydrogen Bonding Stereocontrolling Effect in 2-Iminoaldoses

Matamoros,

Pérez,

Light

et al. 2024

J. Org. Chem.

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The reverse anomeric effect is usually associated with the equatorial preference of nitrogen substituents at the anomeric center. Once postulated as another anomeric effect with explanations ranging from electrostatic interactions to delocalization effects, it is now firmly considered to be essentially steric in nature. Through an extensive research on aryl imines from 2-amino-2-deoxyaldoses, spanning nearly two decades, we realized that such substances often show an anomalous anomeric behavior that cannot easily be rationalized on the basis of purely steric grounds. The apparent preference, or stabilization, of the β-anomer takes place to an extent that not only neutralizes but also overcomes the normal anomeric effect. Calculations indicate that there is no stereoelectronic effect opposing the anomeric effect, resulting from the repulsion between electron lone pairs on the imine nitrogen and the endocyclic oxygen. Such data and compelling structural evidence unravel why the exoanomeric effect is largely inhibited. We are now confident, as witnessed by 2-iminoaldoses, that elimination of the exo-anomeric effect in the α-anomer is due to the formation of an intramolecular hydrogen bond between the anomeric hydroxyl and the iminic nitrogen, thereby accounting for a true electronic effect. In addition, discrete solvation may help justify the observed preference for the β-anomer.

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“…In this context, synthesis of unprecedented congeners is of interest as it may eventuate in the discovery of lead compounds having novel biological activities and pharmaceutical value. Exploiting the unique reactivity of organic compounds in superacid, we report herein a general and straightforward access to rare internal 2- N - C -aryl and C -alkyl (fluorinated) glycosides derived from 2-glycopyranosylamines (Figure ).…”

mentioning

confidence: 99%

HF-Induced Intramolecular C-Arylation and C-Alkylation/Fluorination of 2-Aminoglycopyranoses

et al. 2017

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Internal C-aryl and C-alkyl glycosides derived from 2-aminoglycopyranoses have been synthesized, exploiting a HF-mediated stereoselective intramolecular glycosylation. These conditions are compatible with acetate protecting groups and allow introduction of aromatics with various electronic distributions at the anomeric position. This strategy also provides straightforward entry to original fluorinated sugar-azacycle hybrids via a tandem internal C-glycosylation/fluorination reaction starting from 2-N-allyl/propargyl glycopyranoses. All cyclizations proceed in a 1,2-cis stereocontrolled manner.

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Zur Synthese. von D‐Glucopyrano‐(cis‐2′, 1′‐c)‐l,2,3,4‐tetrahydro‐isochinolinen

Cited by 8 publications

References 8 publications

Reversible inhibitors of .beta.-glucosidase

Reversible inhibitors of .beta.-glucosidase

A True Reverse Anomeric Effect Does Exist After All: A Hydrogen Bonding Stereocontrolling Effect in 2-Iminoaldoses

HF-Induced Intramolecular C-Arylation and C-Alkylation/Fluorination of 2-Aminoglycopyranoses

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