Glycosylation of aromatic amines III: Mechanistic implications of the pH-dependent glycosylation of various aromatic amines (kynurenine, 2′-aminoacetophenone, daptomycin, and sulfamethoxzaole)

Gokhale, Madhushree; Kirsch, Lee E.

doi:10.1002/jps.21769

Cited by 7 publications

(3 citation statements)

References 21 publications

(43 reference statements)

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“…Similar conclusions for this type of reaction have been drawn from theoretical and experimental results for other, simpler systems. 16,17,72 The iminium ion product (E9) involved in the first part of this step has a high free energy relative to the other intermediates of the product of the Schiff base formation; this testifies to the increased chemical reactivity of the nitrogen atom (N3) by effect of major geometric changes during rehybridization to the iminium ion. In addition, the nitrogen carries positive charge and may therefore interact electrostatically with the phosphate anion group in DAPE.…”

Section: Resultsmentioning

confidence: 99%

Reactivity of a Phospholipid Monolayer Model under Periodic Boundary Conditions: A Density Functional Theory Study of the Schiff Base Formation between Phosphatidylethanolamine and Acetaldehyde

2010

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A mechanism for the formation of the Schiff base between an acetaldehyde and an amine-phospholipid monolayer model based on Dmol3/density functional theory calculations under periodic boundary conditions was constructed. This is the first time such a system has been modeled to examine its chemical reactivity at this computation level. Each unit cell contains two phospholipid molecules, one acetaldehyde molecule, and nine water molecules. One of the amine-phospholipid molecules in the cell possesses a neutral amino group that is used to model the nucleophilic attack on the carboxyl group of acetaldehyde, whereas the other has a charged amino group acting as a proton donor. The nine water molecules form a hydrogen bond network along the polar heads of the phospholipids that facilitates very fast proton conduction at the interface. Using periodic boundary conditions afforded proton transfer between different cells. The reaction takes place in two steps, namely, (1) formation of a carbinolamine and (2) its dehydration to the Schiff base. The carbinolamine is the primary reaction intermediate, and dehydration is the rate-determining step of the process, consistent with available experimental evidence for similar reactions. On the basis of the results, the cell membrane surface environment may boost phospholipid glycation via a neighboring catalyst effect.

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Section: Resultsmentioning

confidence: 99%

Reactivity of a Phospholipid Monolayer Model under Periodic Boundary Conditions: A Density Functional Theory Study of the Schiff Base Formation between Phosphatidylethanolamine and Acetaldehyde

2010

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“…The precise mechanism of action of daptomycin remains uncertain, but on the basis of available evidence, several antibacterial killing mechanisms have been proposed that will be discussed herein. − The earliest models postulated that daptomycin operates by inhibiting extracellular polymer synthesis (peptidoglycan, uridine diphosphate- N -acid and acetyl- l -alanine), thereby compromising the integrity of the Gram-positive bacterial cell wall. , In Gram-positive bacteria, lipoteichoic acid (LTA), an integral component of the cytoplasmic membrane, is anchored to the membrane surface and extends into the peptidoglycan cell wall. It has been suggested that daptomycin inhibits LTA biosynthesis, potentially by binding to LTA precursors in the cell wall; however this model has now been disproven in S. aureus and E. faecalis . − …”

Section: Mode Of Antibacterial Actionmentioning

confidence: 99%

Structure–Activity Relationships of Daptomycin Lipopeptides

et al. 2020

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Daptomycin is a calcium-dependent cyclic lipodepsipeptide derived from the soil saprotroph Streptomyces roseosporus, and its antibiotic properties make it a key agent for treatment of drug-resistant Gram-positive infections. It is most commonly used clinically for the treatment of Gram-positive skin and skin structure infections (SSSI), Staphylococcus aureus bacteremia, and right-sided endocarditis infections associated with S. aureus, including methicillin resistant S. aureus (MRSA). It has also been used "off-label" for Enterococcal infections. There has been a tremendous amount of research investigating its mode of action, resistance mechanisms, and biosynthesis of this clinically important antimicrobial agent. Although we cover the latter aspects in detail, the primary focus of this review is to provide the most comprehensive and up-to-date reference for the medicinal chemist on the structure−activity−toxicity of this important class of lipopeptide antibiotics.

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“…These are glycosylation with amines [53][54][55][56], direct glycosylations of aromatic compounds [57] and glycosylation processes, where the corresponding glycals were deployed (For reviews in this field see [58][59][60][61]). These reactions do not follow the general sequence of Scheme 4.1.…”

mentioning

confidence: 99%

Organocatalyzed Glycosylation Reactions of Carbohydrates

Mahrwald¹

2015

SpringerBriefs in Molecular Science

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Several different organocatalyzed glycosylation processes of carbohydrates will be discussed. The results clearly support the concept of the application of unactivated and unprotected carbohydrates in glycosylation processes. By generating hydrogen bridges, which are working during the reaction, the configuration at the anomeric carbon atom can be controlled. Extremely high degrees of stereoselectivities were obtained, depending on the configuration of the carbohydrates deployed.

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Glycosylation of aromatic amines III: Mechanistic implications of the pH-dependent glycosylation of various aromatic amines (kynurenine, 2′-aminoacetophenone, daptomycin, and sulfamethoxzaole)

Cited by 7 publications

References 21 publications

Reactivity of a Phospholipid Monolayer Model under Periodic Boundary Conditions: A Density Functional Theory Study of the Schiff Base Formation between Phosphatidylethanolamine and Acetaldehyde

Reactivity of a Phospholipid Monolayer Model under Periodic Boundary Conditions: A Density Functional Theory Study of the Schiff Base Formation between Phosphatidylethanolamine and Acetaldehyde

Structure–Activity Relationships of Daptomycin Lipopeptides

Organocatalyzed Glycosylation Reactions of Carbohydrates

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