Recent Advances in Chlorination: Novel Reagents and Methods from the Last Decade

Abstract

Chlorinated compounds are vital in organic synthesis, impacting nucleophilic substitutions, β-elimination, and C-H acidity. This review highlights recent advances in (hetero)arene chlorination, focusing on novel reagents and methods developed in the past decade. Traditional electrophilic agents like Cl₂ and PCl₅ have been expanded with new chlorinating agents such as Palau’chlor, as well as electrochemical and photochemical techniques. Biocatalyzed chlorination using FAD-dependent halogenases is also explored. Key trends include green chemistry with eco-friendly chlorine sources like NaCl and HCl. Although nucleophilic chlorination remains rare, electrochemical methods show promising, despite equipment limitations. This review emphasizes significant progress in the last decade towards more sustainable and efficient chlorination strategies.