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

This short review provides an overview on the interactionbetween 1,3,5-triaminobenzene derivatives and different kinds of elec-trophiles. Due to the ambident reactivity of these nucleophiles (i.e., atthe nitrogen atom of the substituents and at the aromatic carbon at-om) different compounds can be obtained. Particular attention is de-voted to the detection, isolation, and characterization of covalent inter-mediates of aromatic substitution, starting from Whelandintermediates until the first detection and characterization of Wheland–Meisenheimer intermediates.1 Introduction2 Reactions between 1,3,5-Triaminobenzene Derivatives andCharged Electrophiles2.1 The Proton as an Electrophile2.2 Arenediazonium Salts as Electrophiles3 Reactions between 1,3,5-Triaminobenzene Derivatives andNeutral Electrophiles3.1 Alkyl Halides as Electrophiles3.2 Acyl Halides and Sulfonyl Chlorides as Electrophiles3.3 Aryl Halides and Heteroaryl Halides as Electrophiles3.4 Polynitroheteroaromatics as Electrophiles4 Conclusion