Fluorinated Radicals in Divergent Synthesis via Photoredox Catalysis.

Area of Science:

• Organic Chemistry
• Fluorine Chemistry
• Photoredox Catalysis

Background:

• Fluorine incorporation is crucial for pharmaceuticals, agrochemicals, and materials, enhancing molecular properties.
• Traditional fluorination methods using hydrogen fluoride (HF) or elemental fluorine (F2) pose significant safety and handling challenges.
• There is a growing need for safer, more accessible, and sustainable fluorination strategies.

Purpose of the Study:

• To explore the reactivity of redox-active fluorinated acids and anhydrides for radical fluoroalkylation.
• To develop photoredox catalytic methods for selective and efficient synthesis of organofluorine compounds.
• To demonstrate switchable divergent synthesis for versatile molecular design.

Main Methods:

• Utilized photoredox catalysis to activate fluorinated acids and anhydrides.
• Investigated reaction parameter tuning (solvent, pressure, concentration, additives) for controlling intermediates.
• Employed spectroscopic, experimental, and computational studies for mechanistic elucidation.

Main Results:

• Achieved selective synthesis of diverse fluorinated compounds (trifluoromethylated ketones, lactones, lactams, esters) with high functional group tolerance.
• Demonstrated switchable divergent synthesis, enabling multiple products from common starting materials.
• Established scalability and operational simplicity of the developed photoredox protocols.

Conclusions:

• Photoredox catalysis offers a powerful and sustainable platform for fluoroalkylation using accessible reagents.
• Switchable divergent synthesis provides an elegant strategy for efficient molecular design and synthesis.
• Mechanistic insights were gained into radical reactivity and the effects of radical polarity.