Nucleophile/Electrophile Combinations in Aromatic Substitution: From Wheland to Wheland–Meisenheimer Intermediates Using Strongly Activated Arenes

Dedicated to Prof. H. Mayr on the occasion of his 70^th birthday

Abstract

This short review provides an overview on the interaction between 1,3,5-triaminobenzene derivatives and different kinds of electrophiles. Due to the ambident reactivity of these nucleophiles (i.e., at the nitrogen atom of the substituents and at the aromatic carbon atom) different compounds can be obtained. Particular attention is devoted to the detection, isolation, and characterization of covalent intermediates of aromatic substitution, starting from Wheland intermediates until the first detection and characterization of Wheland–Meisenheimer intermediates.

1 Introduction

2 Reactions between 1,3,5-Triaminobenzene Derivatives and Charged Electrophiles

2.1 The Proton as an Electrophile

2.2 Arenediazonium Salts as Electrophiles

3 Reactions between 1,3,5-Triaminobenzene Derivatives and Neutral­ Electrophiles

3.1 Alkyl Halides as Electrophiles

3.2 Acyl Halides and Sulfonyl Chlorides as Electrophiles

3.3 Aryl Halides and Heteroaryl Halides as Electrophiles

3.4 Polynitroheteroaromatics as Electrophiles

4 Conclusion

Key words

reaction intermediates - aromatic substitution - triaminobenzenes - electrophiles - nucleophiles - Wheland complexes - Wheland–Meisenheimer intermediates

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