Atropisomeric Indene (AroInd) Libraries: Design, Catalytic Synthesis, and Applications

The development of chiral indenyl metal complexes has been hindered by inefficient synthetic methods, significantly lagging behind the well-established Cp metal complexes. In this study, we present a streamlined and highly efficient synthesis of novel atropisomeric indenes (AtroInds) via asymmetric palladium-catalyzed Suzuki–Miyaura cross-coupling reactions. Leveraging this method, AtroInd libraries, encompassing varying steric and electronic properties, were readily constructed. The resulting AtroInd–Rh(III) complexes were prepared with ease and subjected to comprehensive characterization, revealing exceptional catalytic efficiency in asymmetric catalysis. Computational studies provided profound insights into the reaction pathway and the critical factors governing enantioselectivity, thereby enhancing our mechanistic understanding. This integrated approach not only addresses the prevailing synthetic challenges in the preparation of chiral indenes but also establishes a new paradigm for the design and synthesis of novel ligand libraries through advanced synthetic methodologies.