Recent advances in the direct construction of enantioenriched stereocenters through addition of radicals to internal alkenes.

The development of new synthetic methods involving radical intermediates to control the absolute configuration of newly formed stereocenters has seen unprecedented growth in the past few decades. Despite significant advances in this topic, catalytic asymmetric direct construction of stereocenters through addition of radicals to internal alkenes is of special interest due to its potential to simultaneously build (more than) two consecutive stereogenic centers. Methodologies such as chiral Lewis acid catalysis, organocatalysis, and transition metal catalysis have been successfully leveraged to exert enantiocontrol in this challenging domain. This tutorial review highlights the recent significant progress in the realm of rapidly and conveniently building enantioenriched stereocenters via addition of radicals to internal alkenes, with an emphasis on mechanistic scenarios governing the absolute stereochemistry and unmet challenges in this emerging and promising field.