Transition-Metal-Catalyzed Dehydrogenative (3 + 2) Annulation of Aromatic Compounds: Synthesis of Indenes and Indanes via Dual Functionalization of Benzylic and ortho C-H Bonds.

Intermolecular (3 + 2) annulation emerges as a potent approach for constructing 5-membered carbocycles through the fusion of two distinct components. This synopsis encapsulates recent strides in the realm of transition-metal-catalyzed dehydrogenative (3 + 2) annulation of aromatic hydrocarbons, achieved through the dual functionalization of benzylic and ortho C-H bonds. Encompassing three pivotal strategies, namely, (i) C-H bond activation, (ii) benzylic oxidation, and (iii) π-coordination activation, this review offers an overview of the field's recent developments.