Reference scales for the characterization of cationic electrophiles and neutral nucleophiles.

@article{Mayr2001ReferenceSF,
  title={Reference scales for the characterization of cationic electrophiles and neutral nucleophiles.},
  author={Herbert Mayr and Thorsten Bug and Matthias F. Gotta and Nicole Hering and Bernhard Irrgang and B Janker and Bernhard Kempf and Robert Loos and Armin R. Ofial and Grigoriy Ya. Remennikov and Holger Schimmel},
  journal={Journal of the American Chemical Society},
  year={2001},
  volume={123 39},
  pages={
          9500-12
        }
}
  • H. Mayr, T. Bug, +8 authors H. Schimmel
  • Published 11 September 2001
  • Chemistry, Medicine
  • Journal of the American Chemical Society
Twenty-three diarylcarbenium ions and 38 pi-systems (arenes, alkenes, allyl silanes and stannanes, silyl enol ethers, silyl ketene acetals, and enamines) have been defined as basis sets for establishing general reactivity scales for electrophiles and nucleophiles. The rate constants of 209 combinations of these benzhydrylium ions and pi-nucleophiles, 85 of which are first presented in this article, have been subjected to a correlation analysis to determine the electrophilicity parameters E and… Expand
Determination of the electrophilicity parameters of diethyl benzylidenemalonates in dimethyl sulfoxide: reference electrophiles for characterizing strong nucleophiles.
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TLDR
The kinetics of the reactions of different heterocyclic anions derived from imidazoles, purines, pyrimidines, and related compounds with benzhydrylium ions and structurally related quinone methides have been studied in DMSO and water to determine the nucleophilicity parameters N and s(N) for these anions. Expand
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TLDR
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TLDR
The electrophilicities of the indol-3-ylmethylium ions 3(a-k) were derived and used to predict potential nucleophilic reaction partners and a discrepancy between published rate constants for the reactions of morpholine and piperidine was analyzed and demonstrated to be due to a mistake of the value reported in the literature. Expand
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The rate constants for the reactions of iminium ions with amines and water in acetonitrile are 10(3)-10(5) times faster than predicted by the quoted correlation, which is explained by the transition states which already experience the anomeric stabilization of the resulting N,N- and O, N-acetals. Expand
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Do general nucleophilicity scales exist
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TLDR
The rates of the reactions of the arylsulfonyl-substituted carbanions carrying α-chloro and α-bromo substituents with quinone methides 2a-g and benzylidenemalonates 2h and 2i in DMSO reveal the title compounds to be among the most reactive nucleophiles so far integrated on the authors' comprehensive nucleophilicity scale. Expand
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