Homogenous transition-metal catalysts bearing a chiral ligand are widely used for asymmetric hydrogenation of unsaturated compounds such as olefins and ketones, providing efficient concise access to products with chiral carbon centers. However, distinguishing the re and si prochiral faces of a double bond bearing two substituents that are sterically and electronically similar is challenging for these catalysts. Herein, we report a relay strategy for constructing compounds with a chiral gem-diaryl carbon center by means of a combination of selective arene exchange between 1,1-diarylethylenes or benzophenones with (naphthalene)Cr(CO)3 and subsequent asymmetric hydrogenation. During the hydrogenation, the Cr(CO)3 unit facilitate differentiation of the two prochiral faces of the substrate double bond via formation of a three-dimensional complex with one of the aromatic rings by selective arene exchange. Density functional theory calculations reveal that during the hydrogenation, chromium coordination affected π-π stacking of the substrate and the catalyst ligand, leading to differentiation of the prochiral faces.
© 2023. The Author(s).