Issue 35, 2021

Halogen bond-induced electrophilic aromatic halogenations

Abstract

In recent years, there has been increasing interest in utilising halogen bonds in organic synthesis, especially in aromatic halogenation reactions. N-Halosuccinimides and 1,3-dihalo-5,5-dimethylhydantoins are popular sources of halonium ions due to their ease of handling and low toxicities. Traditionally, these N-haloimides are activated by electrophiles, namely Brønsted and Lewis acids. The recent discovery of possible activation by nucleophilic Lewis base catalysts led to a paradigm shift in aromatic halogenation. Active functional motifs in Lewis base catalysts such as C[double bond, length as m-dash]S, R–S–R1, Ar–S–S–Ar, S[double bond, length as m-dash]O, Ar–NH2, and R2NH+Cl form halogen bonds with the positively charged σ-hole of the halogen atoms: an essential interaction to produce halonium ions. This review highlights the evolution of the two modes of activation. Evidence of halogen bond formation from mechanistic studies of nucleophilic activation is also discussed herein.

Graphical abstract: Halogen bond-induced electrophilic aromatic halogenations

Article information

Article type
Review Article
Submitted
13 Mai 2021
Accepted
09 Jul 2021
First published
04 Aug 2021

Org. Biomol. Chem., 2021,19, 7518-7534

Halogen bond-induced electrophilic aromatic halogenations

W. Lorpaiboon and P. Bovonsombat, Org. Biomol. Chem., 2021, 19, 7518 DOI: 10.1039/D1OB00936B

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