Selectfluor-Promoted Chemoselective Self-Etherification, Oxidation, and Ritter-Type Amidation of Benzhydrols.

Area of Science:

• Organic Chemistry
• Reaction Mechanisms
• Fluorination Chemistry

Background:

• Chemoselective transformations are crucial in organic synthesis.
• Fluorinated sulfur intermediates are reactive species with potential in chemical synthesis.
• Benzhydrols are versatile starting materials for various organic transformations.

Purpose of the Study:

• To investigate the mechanistic role of in situ generated fluorinated sulfur intermediates.
• To explore the chemoselective transformations of benzhydrols using Selectfluor and sulfur reagents.
• To elucidate condition-dependent reaction pathways.

Main Methods:

• Mechanistic investigation using control experiments.
• Exploration of reaction parameter effects (temperature, reagents, solvent).
• Utilizing Selectfluor as an electrophilic fluorine source with various sulfur-containing reagents.

Main Results:

• Selective self-etherification of benzhydrols via fluorinated sulfur species activation.
• Selective oxidation of benzhydrols to benzophenones under altered conditions (higher temperature, carbon disulfide).
• Ritter-type amidation achieved using nitromethane as solvent.

Conclusions:

• Fluorinated sulfur intermediates play a key role in directing chemoselectivity.
• Reaction conditions (temperature, reagents, solvent) dictate the transformation pathway of benzhydrols.
• Plausible mechanisms for etherification, oxidation, and amidation are proposed based on experimental evidence.