Asymmetric Alkylative Difunctionalization of Carbon‐Carbon Double Bonds by Aliphatic C–H Bond Activation

This Concept highlights the latest advancements in asymmetric alkylative difunctionalization of carbon‐carbon double bonds by utilizing aliphatic C–H substrates as alkyl radical precursors. By integrating different hydrogen atom transfer (HAT) process with various transition metal catalytic systems, various alkane substrates can be efficiently converted into corresponding alkyl radicals, which then participate in radical additions to carbon‐carbon double bonds followed by stereoselective functionalizations with a 3rd‐component. These strategies leverage inexpensive, abundant, and readily available alkane feedstocks to rapidly construct complex chiral molecules, demonstrating high step‐ and atom‐economy. This Concept focuses on recent progress and applications of this area, provides a comprehensive perspective on current developments and suggests future directions in alkane‐involved asymmetric transformations.