An Extrusion Strategy for On-Demand SF₅Cl Gas Generation from a Commercial Disulfide

Area of Science:

• Organic Chemistry
• Synthetic Chemistry
• Fluorine Chemistry

Background:

• Chloropentafluorosulfanyl (SF5Cl) is a valuable reagent in organic synthesis.
• Traditional methods for SF5Cl generation and handling pose safety and convenience challenges, often requiring specialized equipment like lecture bottles and gloveboxes.

Purpose of the Study:

• To develop a novel, safer, and more accessible ex situ method for generating SF5Cl.
• To demonstrate the applicability of the generated SF5Cl in various organic transformations.
• To establish a straightforward method for stereochemical analysis of SF5Cl-containing compounds.

Main Methods:

• Ex situ generation of SF5Cl using 4,4'-dipyridyl disulfide as a safe, commercially available reagent.
• Utilizing a two-chamber reactor for controlled SF5Cl generation and application in reactions.
• Employing 1H-19F HOESY (Heteronuclear Overhauser Effect SpectroscopY) for stereochemical determination.

Main Results:

• A novel and safe methodology for the ex situ generation of SF5Cl was successfully established.
• The method allows for the application of SF5Cl in diverse solvents without the need for glovebox techniques.
• The utility of the generated SF5Cl in specific transformations was demonstrated.
• 1H-19F HOESY was validated as a rapid and simple tool for indicating the stereochemistry of chloropentafluorosulfanylated olefins.

Conclusions:

• The developed methodology offers a safer and more practical alternative for accessing SF5Cl in synthetic organic chemistry.
• This approach enhances the accessibility of SF5Cl for various chemical transformations, simplifying experimental procedures.
• The proposed 1H-19F HOESY technique provides an efficient means for stereochemical assignment in relevant fluorinated compounds.