Terminal Selective Arylation of Inert Alkanes via Radical-Organometallic Crossover

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Achieving selectivity in hydrocarbon functionalization, particularly C-H activation of alkanes, is difficult.
• Existing methods often yield complex mixtures favoring branched isomers, with linear selectivity remaining a significant challenge.

Purpose of the Study:

• To develop a mild and direct method for highly linear selective arylation of inert alkanes.
• To overcome the inherent lack of selectivity in alkane C-H functionalization.

Main Methods:

• Combination of photo-hydrogen atom transfer (photo-HAT) and nickel-catalyzed organometallic chainwalking.
• Utilizing a monodentate lutidine ligand to enable radical-organometallic mechanism crossover.

Main Results:

• The first highly linear selective arylation reaction of alkanes reported.
• Demonstrated regioconvergent formation of linear arylation products from various alkanes.
• Monodentate heterocycles identified as privileged ligands for selective C-H functionalization, contrasting with bidentate ligands that yield branched products.

Conclusions:

• The developed method provides a breakthrough in selective alkane functionalization.
• The radical-organometallic crossover mechanism is key to achieving high linearity.
• This work paves the way for controllable and selective functionalization of simple hydrocarbons.