Chapter 10 - Transition metal-catalysed reactions: Diastereoselectivity and asymmetric synthesis

Abstract

This chapter deals with the stereochemistry of transition metal-catalysed reactions and begins with diastereoselective epoxidation. The Sharpless approach to highly efficient asymmetric epoxidation is described in detail with Sharpless mnemonic, mechanism and synthetic applications. The kinetic resolution methodology and extended Sharpless rule are included. The Jacobsen–Katsuki asymmetric epoxidation is presented with a mechanistic model. The hydrolytic kinetic resolution method is included. The Sharpless asymmetric dihydroxylation is described with a predictive model, catalytic cycle and applications. The Sharpless asymmetric aminohydroxylation is presented. Asymmetric hydrogenation of alkenes with chiral rhodium catalysts is described with mechanism and stereochemical models. Noyori asymmetric hydrogenation of alkenes and ketones with chiral ruthenium catalysts is described with mechanistic models and synthetic applications. Asymmetric transfer hydrogenation using a chiral ruthenium complex is presented with the metal–ligand bifunctional mechanism. Finally, asymmetric palladium-catalysed intermolecular and intramolecular Heck reactions and asymmetric Suzuki cross-coupling reaction are described.