Radicals in Stereoselective CC Bond Formation

Abstract

An overview of the most commonly used procedures involving radical reactions for the formation of carbon–carbon bonds, focused on target‐oriented synthesis, is presented. The predominance of substrate‐controlled diastereoselective processes among the examples reflects that asymmetric synthesis of natural products or related compounds via radicals is still challenging despite the progress made in the last decade. Even the application of chiral auxiliaries or chiral Lewis acids as ligands in drug and natural product synthesis has had only limited success. This chapter covers the classic radical chain processes involving atom‐transfer or reductive procedures and nonchain methods using either reductive species, such as Sm(II) or Ti(III), or oxidative Mn(III) derivatives. Furthermore, new improvements in enolate oxidative couplings and the introduction of organocatalysis in radical chemistry are also discussed.