Fluorofunctionalizations of C-C Multiple Bonds and C-H Bonds

Area of Science:

• Organic Chemistry
• Organofluorine Chemistry
• Catalysis

Background:

• Organofluorine compounds are crucial in pharmaceuticals, agrochemicals, and materials due to fluorine's unique properties.
• Developing efficient methods for introducing fluorine-containing groups is a significant research challenge.

Purpose of the Study:

• To detail recent advancements in organofluorine synthesis.
• To showcase new catalytic systems and reaction conditions for fluorination.
• To explore trifluoromethylation and fluorofunctionalization of various substrates.

Main Methods:

• Trifluoromethylation of C-C multiple bonds using Togni reagent and Lewis acid catalysis.
• Asymmetric fluorofunctionalization of alkenes employing a novel phase-transfer catalyst.
• Development of linked binaphthyl dicarboxylate catalysts for enantioselective fluorocyclization and fluorination.
• C-H fluorofunctionalization via catalysis or photoactivation, including benzylic and aromatic C-H trifluoromethylation and Csp3-H fluorination.

Main Results:

• Effective trifluoromethylation of C-C bonds was achieved by activating hypervalent iodine.
• A novel phase-transfer catalyst enabled asymmetric fluorolactonization.
• Highly enantioselective fluorocyclization and deprotonative fluorination of allylic amides were accomplished.
• Rare benzylic trifluoromethylation and aromatic C-H trifluoromethylation under photoirradiation were demonstrated, alongside Csp3-H fluorination.

Conclusions:

• The presented work expands the synthetic toolbox for organofluorine compounds.
• Novel catalysts and methodologies offer precise control over fluorination reactions.
• These advancements hold potential for applications in medicinal chemistry and materials science.