Benzylic Methylene Functionalizations of Diarylmethanes

Diarylmethanes are cardinal scaffolds by virtue of their unique structural feature including the presence of a benzylic CH 2 group that can be easily functionalized to generate a variety of fascinating molecules holding immense importance in pharmaceutical, agrochemical, and material sciences. While the originally developed protocols for benzylic C−H functionalization in diarylmethanes employing base‐mediated and metal‐catalyzed strategies are still actively used, they are joined by a new array of metal‐free conditions, offering milder and benign conditions. With the recent surge of interest towards the synthesis of functionalized diarylmethanes, numerous choices are now available for a synthetic organic chemist to transform the benzylic C−H bond to C−C or C−X bond offering the synthesis of any molecule of choice. This review highlights benzylic methylene (CH 2 ) functionalizations of diaryl/heteroarylmethanes utilizing various base‐mediated, transition‐metal‐catalyzed, and transition‐metal free approaches for the synthesis of structurally diverse important organic molecules, often with a high chemo‐, regio‐ and enantio‐selectivity. This review also attempts to provide analysis of the scope and limitations, mechanistic understanding, and sustainability of the transformations.