[RhCp*Cl(2)](2)-Catalyzed Indole Functionalization: Synthesis of Bioinspired Indole-Fused Polycycles

[Image: see text] Polycyclic fused indoles are ubiquitous in natural products and pharmaceuticals due to their immense structural diversity and biological inference, making them suitable for charting broader chemical space. Indole-based polycycles continue to be fascinating as well as challenging targets for synthetic fabrication because of their characteristic structural frameworks possessing biologically intriguing compounds of both natural and synthetic origin. As a result, an assortment of new chemical processes and catalytic routes has been established to provide unified access to these skeletons in a very efficient and selective manner. Transition-metal-catalyzed processes, in particular from rhodium(III), are widely used in synthetic endeavors to increase molecular complexity efficiently. In recent years, this has resulted in significant progress in reaching molecular scaffolds with enormous biological activity based on core indole skeletons. Additionally, Rh(III)-catalyzed direct C–H functionalization and benzannulation protocols of indole moieties were one of the most alluring synthetic techniques to generate indole-fused polycyclic molecules efficiently. This review sheds light on recent developments toward synthesizing fused indoles by cascade annulation methods using Rh(III)-[RhCp*Cl(2)](2)-catalyzed pathways, which align with the comprehensive and sophisticated developments in the field of Rh(III)-catalyzed indole functionalization. Here, we looked at a few intriguing cascade-based synthetic designs catalyzed by Rh(III) that produced elaborate frameworks inspired by indole bioactivity. The review also strongly emphasizes mechanistic insights for reaching 1–2, 2–3, and 3–4-fused indole systems, focusing on Rh(III)-catalyzed routes. With an emphasis on synthetic efficiency and product diversity, synthetic methods of chosen polycyclic carbocycles and heterocycles with at least three fused, bridged, or spiro cages are reviewed. The newly created synthesis concepts or toolkits for accessing diazepine, indol-ones, carbazoles, and benzo-indoles, as well as illustrative privileged synthetic techniques, are included in the featured collection.