Terminal Selective Arylation of Inert Alkanes via Radical‐Organometallic Crossover
Year: 2025
Type: article
Abstract: Selectivity is an essential part of organic synthesis and key to synthetic efficiency, where it can help reduce energy requirements for product separation, purification, and disposal of low value by-products. However, selectivity is challenging to achieve in hydrocarbon molecules, with C─H functionalization of alkanes almost invariably leading to a complex mixture of products favoring branched isomers and linear selectivity remaining elusive. Herein we report a mild and direct method that combines photo-hydrogen atom transfer (photo-HAT) and nickel catalyzed organometallic chainwalking chemistry to give the first highly linear selective arylation reaction starting from inert alkanes. Key to success is crossover from a radical to organometallic chainwalking mechanism permitted by a monodentate lutidine ligand, allowing an unselective photo-HAT step to be funneled regioconvergently to form the linear arylation product for a variety of alkanes. This result is in sharp contrast to the unselective formation of branched products using bidentate ligands and demonstrates monodentate heterocycles to be a privileged ligand class for selective C─H functionalization. Preliminary mechanistic experiments are consistent with the radical-organometallic crossover mechanism and support it as an important step toward controllable and selective functionalization of simple hydrocarbons.
Source: Chemistry - A European Journal
Institution: Rice University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W4414473039