Synthesis of C <i>sp</i> ³ Chlorinated Compounds from Cyclopropanes, Olefins, and C–H Bonds via Photolysis of Willgerodt-Type Reagents

C<i>sp</i> ³-Cl bonds are essential as diversification handles in organic synthesis and are found in many natural products and bioactive molecules. In this work, we introduce a general protocol for the selective chlorination of aryl cyclopropanes, olefins, and activated C-H bonds using direct photoexcitation of Willgerodt-type reagents to generate chlorine radicals. Preliminary results for an iodine-(I/III) catalytic process starting from abundant chloride salts are also presented. Furthermore, a one-pot protocol has been developed for the telescoped functionalization of benzylic chlorides with C-, N-, O-, and S-nucleophiles. Especially, this approach provides a platform to access 1,1-diaryl motifs, which are important building blocks for the synthesis of pharmacophores.