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
        }
}
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… 

Determination of the electrophilicity parameters of diethyl benzylidenemalonates in dimethyl sulfoxide: reference electrophiles for characterizing strong nucleophiles.

TLDR
Compounds 1 a-i are suitable reference electrophiles for determining the reactivities of highly reactive nucleophiles, such as carbanions with 16 and correlate excellently with Hammett's substituent constants sigma(p).

Nucleophilic reactivities of the anions of nucleobases and their subunits.

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.

Nucleophilicity parameters of enamides and their implications for organocatalytic transformations.

TLDR
The combination of the N and s(N) parameters with the previously reported E parameters of typical Michael acceptors, α,β-unsaturated iminium ions, and the chlorinating agent hexachlorocyclohexa-2,4-dienone allowed us to reliably reproduce the experimental rate constants of the reactions with these electrophiles.

Nucleophilicity Parameters of Stabilized Iodonium Ylides for Characterizing Their Synthetic Potential.

TLDR
The iodonium ylides 1(a-d) thus have nucleophilicities similar to those of pyrroles, indoles, and silylated enol ethers and, therefore, should be suitable substrates in iminium-activated reactions.

Electrophilicities of benzaldehyde-derived iminium ions: quantification of the electrophilic activation of aldehydes by iminium formation.

TLDR
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.

Reactivity of Nitroalkyl Anions Addition to Substituted Benzylidenecyanoacetates: Electrophilicity Parameters and Free Energy Relationships

The kinetics of the reactions of benzylidenecyanoacetates 1a–d (X = H, Me, OMe, and NMe2) with nitroalkyl anions 2a–c have been studied in aqueous solution at 20°C. The second-order rate constants

Do general nucleophilicity scales exist

Comprehensive nucleophilicity scales including π-, n- and σ-nucleophiles have been constructed using benzhydrylium ions and structurally related quinone methides as reference electrophiles. It is

Kinetics of the solvolyses of benzhydryl derivatives: basis for the construction of a comprehensive nucleofugality scale.

A series of 21 benzhydrylium ions (diarylmethylium ions) are proposed as reference electrofuges for the development of a general nucleofugality scale, where nucleofugality refers to a combination of

Nucleophilicity Parameters of Arylsulfonyl-Substituted Halomethyl Anions.

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.

Metal Enolates – Enamines – Enol Ethers: How Do Enolate Equivalents Differ in Nucleophilic Reactivity?

The kinetics of the reactions of trimethylsilyl enol ethers and enamines (derived from deoxybenzoin, indane-1-one, and α-tetralone) with reference electrophiles (p-quinone methides, benzhydrylium and
...

References

SHOWING 1-10 OF 29 REFERENCES

Principles and applications of organotransition metal chemistry

A perspective Bonding Survey of organotransition metal complexes according to ligand Ligand substitution processes Oxidative-addition and reductive elimination Intramolecular insertion reactions

Solvents and Solvent Effects in Organic Chemistry

INTRODUCTION SOLUTE-SOLVENT INTERACTIONS Solutions Intermolecular Forces Solvation Preferential Solvation Micellar Solvation (Solubilization) Ionization and Dissociation CLASSIFICATION OF SOLVENTS

Rates and equilibria of organic reactions as treated by statistical, thermodynamic, and extrathermodynamic methods

Graduate-level text stresses extrathermodynamic approach to quantitative prediction and constructs a logical framework that encompasses and classifies all known extrathermodynamic relationships.

The determination of ionization constants : a laboratory manual

This book should be of interest to organic chemists, biochemists, physical scientists and researchers.

A Dissertation ON

Diplomarbeit

  • Ludwig-Maximilians-Universität München
  • 1999

Diazoalkane : Eigenschaften und Synthesen

Correlation Analysis of Chemical Data

Reaktionen und Synthesen

  • Thieme-Verlag, Stuttgart
  • 1981