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

  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},
  volume={123 39},
  • 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.
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). Expand
Nucleophilic reactivities of the anions of nucleobases and their subunits.
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
Nucleophilicity parameters of enamides and their implications for organocatalytic transformations.
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. Expand
Nucleophilicity Parameters of Stabilized Iodonium Ylides for Characterizing Their Synthetic Potential.
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. Expand
Structure and Reactivity of Indolylmethylium Ions: Scope and Limitations in Synthetic Applications.
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
Electrophilicities of benzaldehyde-derived iminium ions: quantification of the electrophilic activation of aldehydes by iminium formation.
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
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 constantsExpand
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 isExpand
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 ofExpand
Nucleophilicity Parameters of Arylsulfonyl-Substituted Halomethyl Anions.
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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The basic aim of the book is two-fold: to describe routes to functionalized organosilanes and the useful behavior of such silanes, with emphasis placed on the organic moiety; to provide coverage ofExpand
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Graduate-level text stresses extrathermodynamic approach to quantitative prediction and constructs a logical framework that encompasses and classifies all known extrathermodynamic relationships.Expand
The determination of ionization constants : a laboratory manual
This book should be of interest to organic chemists, biochemists, physical scientists and researchers.
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The thesis at hand describes a system for the recognition of predefined situations in buildings. The definition of the situations is based on a hierarchy of symbols, which are also predefined. TheExpand
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