Influence of neighboring phenyl participation on the .alpha.-deuterium isotope effect on solvolysis rates. Neophyl esters

Shiner, V. J.; Seib, R. C.

doi:10.1021/ja00419a051

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Cited by 16 publications

(2 citation statements)

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“…Some time ago, it was observed 4a,b that neophyl triflate solvolyzes slower in 70% TFE than in 97% TFE. This TFE anomaly (increasing rate with decreasing ionizing power)5a was attributed to enhanced ability of TFE to solvate bridged carbocation ion pairs.…”

mentioning

confidence: 99%

Neighboring Group Competition Revisited: Relative Abilities of Cyclobutyl/Cyclopentyl/Phenyl Groups To Stabilize an Electron-Deficient Carbon

Roberts

1999

J. Org. Chem.

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mentioning

confidence: 99%

Neighboring Group Competition Revisited: Relative Abilities of Cyclobutyl/Cyclopentyl/Phenyl Groups To Stabilize an Electron-Deficient Carbon

Roberts

1999

J. Org. Chem.

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“…The application of theories relating to variation in transition-state structure has been greatly simplified by the presentation of potential energy surfaces in terms of the reactive intermediates which could be involved in a mechanism. 76•9•'1" 19 In the present paper we will for the sake of simplicity refer to such diagrams as More O'Ferrall plots,11 although it should be noted that Ingold, 18 Jencks,9 and Thornton76 have also pioneered in their use.…”

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confidence: 99%

Prediction of SN2 transition state variation by the use of More O'Ferrall plots

Harris¹,

Shafer²,

Moffatt³

et al. 1979

J. Am. Chem. Soc.

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Mécanisme de solvolyse des cis‐ et trans‐(p‐toluènesulfonates) d'aryl‐2‐cyclopentyle I. Etude de la première étape de la solvolyse: effets isotopiques de l' atone de deutérium en position 2, effets de sel basique et effet spécial de sel

Ronco

Petit

Guyon

et al. 1988

Helvetica Chimica Acta

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We havc studied the first step of the solvolysis of cis-and trans-2-arylcyclopentyl p-toluenesulfonates in HCOOH, AcOH, and EtOH. All substrates show a high kinetic I-deuterium isotope effect ( / C~/ / C~( ,~ > 1.15). This fact indicates that the first step leads to a classical intimate ion-pair which dissociates to a solvent-separated ion-pair, without participation either of the solvent, the 2-aryl group, or a H-atom at C(2). The slight influence of added basic ions on reaction rate allows us to exclude any direct solvent attack on the covalent substrate even in the most favorable case, i.e. ethanolysis of 2-(p-nitrophenyl)cyclopentyl p-toluenesulfonates. Furthermore, solventseparated ion pair formation is indicated by the special salt effect induced by LiC10,.

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Influence of neighboring phenyl participation on the .alpha.-deuterium isotope effect on solvolysis rates. Neophyl esters

Cited by 16 publications

References 4 publications

Neighboring Group Competition Revisited: Relative Abilities of Cyclobutyl/Cyclopentyl/Phenyl Groups To Stabilize an Electron-Deficient Carbon

Neighboring Group Competition Revisited: Relative Abilities of Cyclobutyl/Cyclopentyl/Phenyl Groups To Stabilize an Electron-Deficient Carbon

Prediction of SN2 transition state variation by the use of More O'Ferrall plots

Mécanisme de solvolyse des cis‐ et trans‐(p‐toluènesulfonates) d'aryl‐2‐cyclopentyle I. Etude de la première étape de la solvolyse: effets isotopiques de l' atone de deutérium en position 2, effets de sel basique et effet spécial de sel

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