The hydrolytic reactivity of β-sultams

Baxter, Nicholas J.; Laws, Andrew P.; Rigoreau, Laurent; Page, Michael I.

doi:10.1039/p29960002245

Cited by 29 publications

(39 citation statements)

References 24 publications

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“…This is similar in magnitude to the enhancement of at least 10 7 previously reported for -sultams compared with analogous sulfonamides. 9,10 The N-acyl -sultam 3 is also 10 3 -fold more reactive than the analogous N-acyl -lactam 7, similar to the difference observed for N-alkyl -sultams and -lactams. 9 The pH-rate profile for the hydrolysis of N-benzyl 4,4-dimethyl-3-oxo--sultam 4 is shown in Figure 1 and displays a base-catalyzed reaction as well as a pH-independent pathway.…”

supporting

confidence: 66%

Acyl vs Sulfonyl Transfer in N-Acyl β-Sultams and 3-Oxo-β-sultams

2003

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[reaction: see text] N-Acylsulfonamides usually react with nucleophiles by acyl transfer and C-N bond fission. However, the hydrolysis of N-acyl beta-sultams is a sulfonyl transfer reaction that occurs with S-N fission and opening of the four-membered ring. Similar to other beta-sultams, the N-acyl derivatives are at least 10(6)-fold more reactive than N-acyl sulfonamides. 3-Oxo-beta-sultams are both beta-lactams and beta-sultams but also hydrolyze with preferential S-N bond fission.

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confidence: 66%

Acyl vs Sulfonyl Transfer in N-Acyl β-Sultams and 3-Oxo-β-sultams

2003

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“…Furthermore, -sultams are 10 2 -10 3 -fold more reactive than corresponding -lactams, compared with the 10 4 -fold slower rate of alkaline hydrolysis of acyclic sulfonamides compared with analogous amides. 12 This is the first example of the rate of sulfonyl transfer being greater than that of the corresponding acyl reaction.…”

Section: Hydrolysis Of B-sultamsmentioning

confidence: 87%

Comparison of the mechanisms of reactions of β‐lactams and β‐sultams, including their reactions with some serine enzymes

Page

Tsang

Ahmed

2006

J of Physical Organic Chem

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The strain energy of the four-membered ring of -lactams is not released in the transition state to lower the activation energy of reactions involving ring-opening. The alkaline hydrolysis of N-aroyl -lactams occurs with competitive exo-and endocyclic C-N ring fission, the ratio of which varies with the aryl substituent. -Sultams are four-membered cyclic sulfonamides and are about 10 3 fold more reactive than analogous -lactams. Nucleophiles usually attack N-acylsulfonamides at the carbonyl centre resulting in C-N bond fission, but the hydrolysis of N-acyl -sultams occurs with S-N fission and opening of the four-membered ring. The 3-oxo--sultams are a unique combination of both -lactams and -sultams and therefore are susceptible to nucleophilic attack at either the acyl or the sulfonyl centre, but they hydrolyse with exclusive S-N bond fission. -Sultams are novel inhibitors of the serine enzymes elastase, transpeptidase and -lactamase due to sulfonylation of the active-site serine residue. Structureactivity relationships are used to identify differences in transition-state structures between -sultams as inhibitors and -lactams as substrates.

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“…[200] Recently,D oughertya nd co-workers have presented ag eneral strategy for the direct photoinduced decay of quinonebased TML systems. [202,203] The fact that quinone moieties can be photochemically reduced to their corresponding dihydroquinones is long known, [204][205][206][207] and severale xamples for which photoreduction is mediated by an adjacent sulfide [208,209] or amine [210][211][212][213][214][215][216][217] functionhave been reported.…”

Section: Photosensitive Tml Systemsmentioning

confidence: 99%

Trimethyl Lock: A Multifunctional Molecular Tool for Drug Delivery, Cellular Imaging, and Stimuli‐Responsive Materials

Okoh

Klahn

2018

ChemBioChem

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Trimethyl lock (TML) systems are based on ortho-hydroxydihydrocinnamic acid derivatives displaying increased lactonization reactivity owing to unfavorable steric interactions of three pendant methyl groups, and this leads to the formation of hydrocoumarins. Protection of the phenolic hydroxy function or masking of the reactivity as benzoquinone derivatives prevents lactonization and provides a trigger for controlled release of molecules attached to the carboxylic acid function through amides, esters, or thioesters. Their easy synthesis and possible chemical adaption to several different triggers make TML a highly versatile module for the development of drug-delivery systems, prodrug approaches, cell-imaging tools, molecular tools for supramolecular chemistry, as well as smart stimuliresponsive materials.

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The hydrolytic reactivity of β-sultams

Cited by 29 publications

References 24 publications

Acyl vs Sulfonyl Transfer in N-Acyl β-Sultams and 3-Oxo-β-sultams

Acyl vs Sulfonyl Transfer in N-Acyl β-Sultams and 3-Oxo-β-sultams

Comparison of the mechanisms of reactions of β‐lactams and β‐sultams, including their reactions with some serine enzymes

Trimethyl Lock: A Multifunctional Molecular Tool for Drug Delivery, Cellular Imaging, and Stimuli‐Responsive Materials

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