Practical synthesis of Csp3 Chlorinated Compounds from Cyclopropanes, Olefins and C-H Bonds via photolysis of Willgerodt-type reagents

Csp3-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 the direct photoexcitation of Willgerodt-type reagents to generate chlorine radicals. Preliminary results on 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.