The catalytic enantioselective hydrogenation of prochiral olefins is a key reaction in asymmetric synthesis. Its relevance applies to both industry and academia as an inherently direct and sustainable strategy to induce chirality. Here we briefly recount the early breakthroughs concerning the asymmetric hydrogenation of largely unfunctionalized olefins, from the first reports to the advent of chiral Crabtree-like catalysts. The mechanism and its implications on the enantioselectivity are shortly discussed. The main focus of this Perspective lies on the more recent advances in the field, such as the latest developed classes of ligands and the opportunity to employ more Earth-abundant metals. Therefore, separate sections consider iridium N,P-, NHC-, P,S-, and O,P-catalysts, and rhodium, palladium, cobalt, and iron catalysts. Finally, the remaining unsolved challenges are examined, and the potential directions of forthcoming research are outlined.

In the asymmetric hydrogenation of olefins the enantiodivergent outcome is predominant. However, the less common enantioconvergent phenomenon affords significant practical advantages, such as the possibility to hydrogenate mixtures of E/Z alkenes.

The renewed interest in electrosynthesis demonstrated by organic chemists in the last years has allowed for rapid development of new methodologies. In this review, advances in enantioselective electrosynthesis that rely on catalytic amounts of organic or metal-based chiral mediators are highlighted with focus on the most recent developments up to July 2020. Examples of C-H functionalization, alkene functionalization, carboxylation and cross-electrophile couplings are discussed, along with their related mechanistic aspects.

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Kinetic analysis was used as a tool for rational optimization of a catalytic, direct substitution of alcohols to enable the selective formation of unsymmetrical ethers, thioethers, and Friedel-Crafts alkylation products...