Utilizing the σ-complex stability for quantifying reactivity in nucleophilic substitution of aromatic fluorides

Utilizing the σ-complex stability for quantifying reactivity in nucleophilic substitution of aromatic fluorides

A computational approach using density functional theory to compute the energies of the possible σ-complex reaction intermediates, the "σ-complex approach", has been shown to be very useful in predicting regioselectivity, in electrophilic as well as nucleophilic aromatic substitution. In this article we give a short overview of the background for these investigations and the general requirement...

Modern Nucleophilic Aromatic Substitution

CAN WE PREDICT REACTIVITY FOR AROMATIC NUCLEOPHILIC SUBSTITUTION WITH (1sFJFLUORIDE ION?

The correlation between the 1%-NMR chemical shift of the aromatic ring carbon bearing the leaving group and the yield of nucleophilic aromatic displacement with no-carrier-added [ 18Flfluoride ion was evaluated. In comparison of structurally analogous compounds (fluoro, nitro and trimethylammonium substituted benzaldehydes, benzophenones and benzonitriles), the 13C-NMR chemical shift of the rea...

On the frontier between nucleophilic aromatic substitution and catalysis.

A study on the arylation of heteroatom nucleophiles by using activated haloarenes, with or without metal catalysts, is reported. A discussion concerning the involvement of traces of metals is presented, supported by an unexpected ''ligand'' effect in the absence of added metal catalysts. We believe that the frontier between nucleophilic aromatic substitution and catalysis will likely prove to b...

Synthesis of polynitroxides based on nucleophilic aromatic substitution.

The scope and limitations of the synthesis of polynitroxides by nucleophilic substitution of electron-deficient fluorinated aromatic compounds are described. The method provides a facile route to the formation of polynitroxides exhibiting strong electron exchange between nitroxide groups.