Oxidative Chlorination: A Sustainable Alternative for the Preparation of Chloroarenes

Chloroarenes are important from both academic and industrial points of view. They are useful intermediates and building blocks in manufacturing a range of bulk and fine aromatic chemicals, dyes, flame retardants in electronic boards, disinfectants, and pharmaceutical drugs. In addition, diverse agrochemicals, synthetic drugs, and natural products are chloroarenes. Although conventional chlorination of arenes is a well-established transformation that has been studied in detail in many textbooks, current challenges have driven scientists to design new strategies that can address the need for efficiency and sustainability. The oxidative chlorination reaction proceeds via an oxidation step of the chloride ion to generate the active electrophilic chlorenium species in situ. In these regards, the present review focused on the main achievementsof the oxidative chlorination of arenes, with special focus on their generality and green aspects. Therefore, the use of different oxidants (hydrogen peroxide, oxygen, iodine(III) reagents, enzymes) and conditions of electrochemistry and photocatalysis are presented.