Dual Photoredox/Copper Catalyzed Fluoroalkylative Alkene Difunctionalization

Area of Science:

• Organic Chemistry
• Fluorine Chemistry
• Photocatalysis

Background:

• Radical difunctionalization of alkenes is crucial for synthesizing complex organic molecules.
• Incorporating fluorine atoms enhances molecular properties, making fluorinated compounds highly sought after.
• Developing efficient methods for selective C-F bond formation remains a challenge.

Purpose of the Study:

• To develop a novel photoredox-catalyzed method for the radical difunctionalization of alkenes.
• To utilize fluorinated halides and nucleophilic components (thiolate and iodide anions) for C-S and C-I bond formation.
• To enable subsequent transformations of the primary products for diverse fluorinated compound synthesis.

Main Methods:

• Photoredox generation of fluorinated radicals from fluorinated halides.
• Radical addition to alkene double bonds.
• Copper-promoted C-S or C-I bond formation.
• Subsequent coupling reactions with silyl enol ethers, α-(trifluoromethyl)styrenes, and trimethylsilyl cyanide.

Main Results:

• Successful radical difunctionalization of alkenes using fluorinated halides.
• Formation of C-S and C-I bonds via copper catalysis.
• Generation of diverse fluorinated compounds through sequential transformations.
• Demonstration of the versatility of the generated primary products in further coupling reactions.

Conclusions:

• The developed method provides an efficient route to various fluorinated compounds.
• The nucleophilic fragments act as redox-active groups, facilitating further synthetic manipulations.
• This approach expands the toolkit for constructing fluorinated organic molecules with potential applications in pharmaceuticals and materials science.