Reactivity and the mechanisms of reactions of β-sultams with nucleophiles

J. Matthew Wood, Paul S. Hinchliffe, Andrew P. Laws, Michael I. Page

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Ethane-1,2-sultam has a pKa of 12.12 ± 0.06 at 30°C and its rate of alkaline hydrolysis shows a pH-dependence reflecting this so that the observed pseudo first-order rate constant at pHs above the pKa are pH independent. There is no evidence of neighbouring group participation in the hydrolysis of either N-α-carboxybenzylethane-1,2-sultam or N-(hydroxyaminocarbonylmethyl)-2-benzylethane-1,2-sultam. Oxyanions, but not amines or thiols, react with N-benzoylethane-1,2-sultam in water by a nucleophilic ring opening reaction confirmed by product analysis and kinetic solvent isotope effects. A Brønsted plot for this reaction has two distinct correlations with βnuc = 0.52 and 0.65 for weak and strong bases, respectively, although a statistically corrected plot may indicate a single correlation.

LanguageEnglish
Pages938-946
Number of pages9
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number5
Early online date18 Mar 2002
DOIs
Publication statusPublished - 21 May 2002

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Nucleophiles
Hydrolysis
Ethane
Sulfhydryl Compounds
Isotopes
Amines
Byproducts
Rate constants
Kinetics
beta-sultam
naphthosultone
Water

Cite this

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abstract = "Ethane-1,2-sultam has a pKa of 12.12 ± 0.06 at 30°C and its rate of alkaline hydrolysis shows a pH-dependence reflecting this so that the observed pseudo first-order rate constant at pHs above the pKa are pH independent. There is no evidence of neighbouring group participation in the hydrolysis of either N-α-carboxybenzylethane-1,2-sultam or N-(hydroxyaminocarbonylmethyl)-2-benzylethane-1,2-sultam. Oxyanions, but not amines or thiols, react with N-benzoylethane-1,2-sultam in water by a nucleophilic ring opening reaction confirmed by product analysis and kinetic solvent isotope effects. A Br{\o}nsted plot for this reaction has two distinct correlations with βnuc = 0.52 and 0.65 for weak and strong bases, respectively, although a statistically corrected plot may indicate a single correlation.",
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Reactivity and the mechanisms of reactions of β-sultams with nucleophiles. / Wood, J. Matthew; Hinchliffe, Paul S.; Laws, Andrew P.; Page, Michael I.

In: Journal of the Chemical Society, Perkin Transactions 2, No. 5, 21.05.2002, p. 938-946.

Research output: Contribution to journalArticle

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AB - Ethane-1,2-sultam has a pKa of 12.12 ± 0.06 at 30°C and its rate of alkaline hydrolysis shows a pH-dependence reflecting this so that the observed pseudo first-order rate constant at pHs above the pKa are pH independent. There is no evidence of neighbouring group participation in the hydrolysis of either N-α-carboxybenzylethane-1,2-sultam or N-(hydroxyaminocarbonylmethyl)-2-benzylethane-1,2-sultam. Oxyanions, but not amines or thiols, react with N-benzoylethane-1,2-sultam in water by a nucleophilic ring opening reaction confirmed by product analysis and kinetic solvent isotope effects. A Brønsted plot for this reaction has two distinct correlations with βnuc = 0.52 and 0.65 for weak and strong bases, respectively, although a statistically corrected plot may indicate a single correlation.

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