In Situ Triflation‐Tandem Cross‐Coupling Enables Synthesis and Photophysical Studies of Indenones and Benzofulvenes

Abstract Indan‐1,3‐diones stand as versatile precursors to a plethora of complex molecules with wide applications; however, their direct cross‐coupling methodologies remain largely unexplored. Herein, we unveil an in situ triflation‐tandem cross‐coupling strategy to synthesize a diverse variety of indenones and benzofulvenes from indan‐1,3‐diones. The successful synthesis of a neolignan natural product and the key intermediate of Indatraline (antidepressant) showcased the synthetic utility of the methodology. The strategy enabled tuning the electronic characteristics of indenones and benzofulvenes, modulating the HOMO‐LUMO gaps. The photophysical properties of these molecules were studied, and the experimental results were compared with the predictions obtained from the DFT studies.