Escape from Flatland: Exploring the Three-Dimensional Chemical Structure Space of Heterocyclic Rings – Diastereoselective Rhodium-Catalyzed Hydrogenation Reactions

This work describes the chemical escape from flatland. The direct hydrogenation of aromatic systems is a compelling tool to access saturated carbo- and heterocycles, an omnipresent motif in natural products, pharmaceuticals, and agrochemicals. The product heterocycles were obtained by hydrogenation in the presence of a homogenous rhodium complex in high yields with moderate to high diastereoselectivities exhibiting the hydrogen atoms in an all-cis arrangement. The high tolerance towards functional groups enables the formation of valuable saturated products, which offer a starting point for further derivatization. This work paves the way for the application in the total synthesis of biologically active natural products.