Benzylic Methylene Functionalizations of Diarylmethanes.

Diarylmethanes are cardinal scaffolds by virtue of their unique structural feature including the presence of a benzylic CH2 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 (CH2 ) 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.